Aqueous resin dispersion, method for its production, coating material and laminate

ABSTRACT

To provide an aqueous dispersion of a resin wherein dispersed particles are stable with fine particle sizes and whereby bleeding out is suppressed, which is thus useful as e.g. a surface treating agent for a polyolefin substrate, an adhesive or a coating material. 
     A resin dispersion having dispersed in water a polymer (C) having a hydrophilic polymer (B) bonded to a polyolefin (A) in a ratio of (A):(B)=100:5 to 100:500 (weight ratio); a method for producing the resin dispersion; and a coating material and a laminate, employing it.

This is a divisional application of U.S. application Ser. No.11/916,384, filed Dec. 3, 2007, which is a 371 of PCT/JP06/311120 filedon Jun. 2, 2006.

TECHNICAL FIELD

The present invention relates to an aqueous resin dispersion containinga polyolefin resin, a coating material containing it, a laminate and amethod for producing the aqueous resin dispersion.

BACKGROUND ART

Polyolefins such as propylene polymers or propylene-α-olefin copolymersare inexpensive and yet excellent in mechanical properties, heatresistance, chemical resistance, water resistance, etc., and thus, theyare used in various fields. However, such polyolefins have no polargroups in their molecules and thus are usually of low polarity anddifficult to bond or apply for coating, and their improvements have beendesired. Accordingly, various treatments have been tried such aschemical treatment of the surface of a polyolefin molded product with areagent or the like, or oxidation treatment of the surface of a moldedproduct by such a means as corona discharge treatment, plasma treatmentor flame treatment. However, such methods not only require specialapparatus but also the effects for improving the coating property or theadhesive property have not been necessarily adequate.

Therefore, in an attempt to impart a good coating property or adhesiveproperty to a polyolefin such as a propylene polymer by a relativelysimple method, a so-called chlorinated polypropylene or an acid-modifiedpropylene-α-olefin copolymer, and further an acid-modified chlorinatedpolypropylene have been developed. Such a modified polyolefin is appliedto the surface of a polyolefin molded product as a surface treatingagent, an adhesive or a coating material. The modified polyolefin isusually applied in the form of a solution in an organic solvent or adispersion in water. With a view to safety and health, and reduction ofenvironment pollution, an aqueous dispersion is usually preferablyemployed.

For example, an aqueous resin dispersion having an acid-modifiedchlorinated polypropylene hydrophilically modified by using a surfactantand a basic substance (JP-A-3-182534) or an aqueous resin dispersionhaving an acid-modified polyolefin hydrophilically modified by using asurfactant and a basic substance (JP-A-6-256592 (U.S. Pat. No.5,534,577), JP-A-2004-002842 (US2005-124753)) may be mentioned. However,such a method has had a problem that in order to make dispersed particlesizes to be fine, it is required to add a large amount of a surfactant,and consequently, a coating material employing such an aqueousdispersion is poor in water resistance or chemical resistance. Further,after coating, the surfactant may sometimes bleed out on the coatedsurface, thus leading to a defective appearance. Thus, a furtherimprovement has been desired.

Further, there is an aqueous resin dispersion having dispersed in watera polymer having functional segments block-copolymerized to polyolefinsegments (JP-A-2001-288372 (US2003-055179). However, the dispersedparticle sizes can not be said to be sufficiently fine, and it is notpossible to form the dispersion without using a surfactant at all, and afurther improvement has been desired.

Further, in a case where the above-mentioned modified polyolefin is tobe used as a water base paint or ink, in order to satisfy theperformance other than the adhesion, it is common to incorporate abinder resin such as an acrylic resin, a polyurethane resin, a polyesterresin, a vinyl acetate resin or an epoxy resin, or a pigment such astitanium oxide or carbon black, as the case requires. However, suchcomponents usually do not have high adhesion to a propylene polymersubstrate, and accordingly, there is a problem such that even if thepropylene polymer resin itself may have a sufficient substrate adhesion,after mixing, the substrate adhesion substantially decreases.

Therefore, there is a case of a water base paint wherein an ethylenepolymer resin having a small particle size is incorporated to a binderresin such as an acrylic resin (JP-A-2004-083787). However, as comparedwith such an ethylene polymer, with a propylene polymer, emulsificationis further difficult, and with respect to a water base paint containinga propylene polymer, it has been strongly desired to solve theabove-mentioned problem.

On the other hand, a polyolefin has a low polarity as mentioned aboveand is thus difficult to emulsify. It has been attempted to emulsify itby using a large amount of a surfactant, or to make the particle size tobe fine by using a special emulsifier. For example, an emulsion having amodified polyolefin dissolved in e.g. an aromatic solvent andhydrophilically modified by using a basic substance or a surfactant(JP-A-01-256556) or a method for producing an aqueous resin compositionemploying an emulsifying machine having a special finely pulverizingmechanism (JP-A-11-269206) has been proposed. However, in the methoddisclosed in JP-A-01-256556, the dispersed particle sizes of theemulsion are as large as from 0.5 to 7 μm, whereby there has been aproblem from the viewpoint of the dispersion stability. Further, in themethod disclosed in JP-A-11-269206, a special emulsifying machine isemployed, where the cost will increase, and practically, a surfactant ora basic substance is essentially required, and there has been a problemthat the particle size of the aqueous dispersion is limited to a levelof about 0.15 μm, and the blending property is poor when blended with anemulsion having a finner particle size.

As a method to make the dispersed particle size to be fine, a method hasalso been proposed wherein a modified polyolefin is dissolved in anether solvent such as propylene glycol monopropyl ether, and water isdropwise added and dispersed in the presence of a base, whereupon thesolvent is distilled off (JP-A-2004-018659 (US2005-143527)). However,such an ether solvent is compatible infinitely with water at a commonlyemployed temperature of from room temperature to the boiling point,whereby water and the ether can not be separated by liquid-liquidseparation after the distillation. Accordingly, the distilled solvent isrequired to be entirely recovered by distillation, thus leading toproblems from the environmental and process aspects. Or, a highlyhydrophobic polyolefin has a low solubility in an ether solvent and ishardly soluble unless it is in a state having polar groups added to thepolyolefin to some extent. Therefore, there is a problem such that anether solvent can not be used as a solvent for a polymerization reactionor a modifying reaction of a polyolefin.

DISCLOSURE OF THE INVENTION Means to Solve Problems

The present inventors have conducted an expensive research to solve theabove-described problems and has arrived at the present invention. Thepresent invention includes the following first, second, third and fourthembodiments.

Namely, the first embodiment of the present invention is based on adiscovery such that a resin dispersion having excellent characteristicscan be obtained by bonding a hydrophilic polymer in a prescribed ratioto a polyolefin and dispersing such a polyolefin in water and providesthe following 1 to 18. Further, the second embodiment of the presentinvention is based on a discovery such that an aqueous resin dispersionhaving a polymer containing a propylene polymer and a specific resindispersed respectively in water, wherein they are in a specificrelation, has an excellent adhesion to a polyolefin substrate andexcellent moisture resistance and oil resistance, and provides thefollowing 19 to 35. Further, the third embodiment of the presentinvention is based on a discovery such that such an excellent aqueousresin dispersion can simply be produced by dissolving a modifiedpolyolefin in a small amount of a solvent which can be mixed with water,then dropwise adding water to disperse the modified polyolefin, followedby distilling off the solvent, and provides the following 36 to 39.Further, the fourth embodiment of the present invention is based on sucha discovery that such an excellent aqueous resin dispersion can simplybe produced by dropwise adding a mixed solvent of a hydrophilic solventand water to a solution having a modified polyolefin dissolved in a goodsolvent to disperse the modified polyolefin, and distilling off the twotypes of solvents, and provides the following 40 to 53.

1. An aqueous resin dispersion having dispersed in water a polymer (C)having a hydrophilic polymer (B) bonded to a polyolefin (A) in a ratioof (A):(B)=100:5 to 100:500 (weight ratio).

2. The aqueous resin dispersion, wherein the polymer (C) is dispersed inwater with its 50% particle diameter of at most 0.5 μm.

3. The aqueous resin dispersion, wherein the polymer (C) is dispersed inwater with its 50% particle diameter of at most 0.2 μm.

4. The aqueous resin dispersion, which contains a surfactant in anamount of at most 10 parts by weight per 100 parts by weight of thepolymer (C).

5. The aqueous resin dispersion, wherein the polyolefin (A) containssubstantially no chlorine.

6. The aqueous resin dispersion, wherein the hydrophilic polymer (B) isbonded in an amount of from 0.01 to 5 mmol per 1 g of the polyolefin(A).

7. The aqueous resin dispersion, wherein the polyolefin (A) is astereo-block polypropylene polymer having isotactic blocks and atacticblocks and having a propylene content of at least 50 mol %, and/or apropylene-α-olefin copolymer.

8. The aqueous resin dispersion, wherein the polyolefin (A) has at leastone member selected from the group consisting of a carboxylic acidgroup, a dicarboxylic anhydride group and a dicarboxylic anhydridemonoester group.

9. The aqueous resin dispersion, wherein the polymer (C) is a graftcopolymer having the hydrophilic polymer (B) graft-bonded to thepolyolefin (A).

10. The aqueous resin dispersion, wherein the hydrophilic polymer (B) isa polyether resin.

11. The aqueous resin dispersion, wherein the hydrophilic polymer (B)has at least one reactive group per molecule.

12. The aqueous resin dispersion, wherein the hydrophilic polymer (B)has at least an amino group as the reactive group.

13. A method for producing an aqueous resin dispersion having dispersedin water a polymer (C) having a hydrophilic polymer (B) bonded to apolyolefin (A) in a ratio of (A):(B)=100:5 to 100:500 (weight ratio),which comprises preparing a mixture of the polymer (C), water and asolvent other than water, and then, removing the solvent from themixture to obtain the resin composition.

14. The method for producing an aqueous resin dispersion, wherein thepolymer (C) is dissolved in the solvent other than water, and then,water is added to prepare the mixture.

15. A coating material made of the aqueous resin dispersion.

16. A laminate having formed on a thermoplastic resin-molded product (F)a layer comprising a polymer (C) having a hydrophilic polymer (B) bondedto a polyolefin (A) in a ratio of (A):(B)=100:5 to 100:500 (weightratio).

17. A laminate having a resin layer formed by applying and heating theaqueous resin dispersion or the coating material, on a thermoplasticresin-molded product (F).

18. A method for producing a laminate, which comprises forming a resinlayer by applying and heating the aqueous resin dispersion or thecoating material, on a thermoplastic resin-molded product (F).

19. An aqueous resin dispersion which has particles made of a polymer(IC) containing a propylene polymer (IA) and particles made of at leastone resin (ID) selected from the group consisting of an acrylic resin, apolyester resin, a polyurethane resin, an epoxy resin and a vinyl esterresin, respectively dispersed in water, and which satisfies thefollowing (1) to (4):

(1) the weight ratio of the propylene polymer (IA) to the resin (ID) isfrom 90:10 to 10:90,

(2) the weight ratio of the total amount of the polymer (IC) and theresin (ID) to water is from 5:95 to 60:40,

(3) the content of a surfactant is at most 10 parts by weight per 100parts by weight of the total amount of the polymer (IC) and the resin(ID), and

(4) the 50% particle diameter of the particles made of the polymer (IC)is at most 0.5 μm and at most 0.9 time of the 50% particle diameter ofthe particles of the resin (ID).

20. The aqueous resin dispersion, wherein the polymer (IC) is a polymerhaving a hydrophilic polymer (IB) bonded to the propylene polymer (IA)in a ratio of (IA):(IB)=100:5 to 100:500 (weight ratio).

21. The aqueous resin dispersion, wherein the polymer (IC) is a polymerhaving the hydrophilic polymer (IB) bonded in an amount of from 0.01 to5 mmol per 1 g of the propylene polymer (IA).

22. The aqueous resin dispersion, wherein the polymer (IC) is a graftcopolymer having a hydrophilic polymer (IB) graft-bonded to thepropylene polymer (IA).

23. The aqueous resin dispersion, wherein the polymer (IC) is a polymerhaving a carboxylic acid derivative group bonded to the propylenepolymer (IA) in an amount of from 0.01 to 5 mmol/g as calculated as agroup represented by —C(═O)O— and wherein the hydrophilic polymer (IB)is bonded to the carboxylic acid derivative group.

24. The aqueous resin dispersion, wherein the hydrophilic polymer (IB)is a polyether resin having an amino group.

25. The aqueous resin dispersion, wherein the polymer (IC) is one havinga carboxylic acid derivative group bonded to the propylene polymer (IA).

26. The aqueous resin dispersion, wherein the propylene polymer (IA) isa stereo-block polypropylene polymer having isotactic blocks and atacticblocks.

27. The aqueous resin dispersion, wherein the propylene polymer (IA) isa stereo-block polypropylene polymer containing isotactic blocks andatactic blocks, and when peaks derived from the carbon atom of a methylgroup of a propylene unit chain portion of a head-to-tail linkage, areobserved by ¹³C-NMR and the chemical shift of a peak top of a peakattributable to a pentad represented by mmmm is set to be 21.8 ppm, theratio (S₁/S) of the area S₁ of a peak having a peak top at 21.8 ppm tothe total area S of peaks appearing from 19.8 ppm to 22.1 ppm, is from20% to 70%, and when the area of a peak (mmmr) having a peak top from21.5 to 21.7 ppm is represented by S₂, 4+2S₁/S₂>5.

28. The aqueous resin dispersion, wherein the propylene polymer (IA) isa propylene-1-butene copolymer having a propylene content of from 50 mol% to 95 mol %, and the copolymer (IA) has a molecular weightdistribution Mw/Mn of at most 3.0 and a melting point Tm of at most 120°C.

29. The aqueous resin dispersion, wherein the propylene polymer (IA) isproduced by using a metallocene catalyst.

30. The aqueous resin dispersion, which further contains a pigment (IE),wherein the weight ratio of the total amount of the polymer (IC) and theresin (ID) to the pigment (IE) is from 100:10 to 100:400.

31. A method for producing an aqueous resin dispersion, which comprisesmixing a dispersion having dispersed in water a polymer (IC) having ahydrophilic polymer (IB) bonded to a propylene polymer (IA) in a ratioof (IA):(IB)=100:5 to 100:500 (weight ratio) and a dispersion havingdispersed in water at least one resin (ID) selected from the groupconsisting of an acrylic resin, a polyester resin, a polyurethane resin,an epoxy resin and a vinyl ester resin, to obtain an aqueous resindispersion wherein the weight ratio of the propylene polymer (IA) to theresin (ID) is from 90:10 to 10:90, and the weight ratio of the totalamount of the polymer (IC) and the resin (ID) to water is from 5:95 to60:40.

32. A coating material made of the aqueous resin dispersion.

33. A method for producing a laminate, which comprises forming a resinlayer by applying and heating the aqueous resin dispersion or thecoating material, on a thermoplastic resin-molded product (F).

34. A laminate having formed on a thermoplastic resin-molded product(IF) a layer comprising a polymer (IC) containing a propylene polymer(IA) and at least one resin (ID) selected from the group consisting ofan acrylic resin, a polyester resin, a polyurethane resin, an epoxyresin and a vinyl ester resin in a weight ratio of (IA):(ID)=90:10 to10:90 and having a surfactant content of at most 10 parts by weight per100 parts by weight of the total amount of the polymer (IC) and theresin (ID).

35. A laminate having a resin layer formed by applying and heating theaqueous resin dispersion or the coating material, on a thermoplasticresin-molded product (IF).

36. A method for producing an aqueous resin dispersion, which is amethod for producing a resin dispersion comprising a modified polyolefinand water, and which comprises a dissolving step of dissolving themodified polyolefin in a solvent (a) wherein the solubility of water at20° C. is from 1.0 to 95.0 wt %, a dispersing step of adding waterthereto, followed by dispersing, and a distillation step of distillingoff at least the solvent (a).

37. The method for producing an aqueous resin dispersion, wherein thesolvent (a) is an alcohol, a ketone or an ester.

38. The method for producing an aqueous resin dispersion, wherein thedissolving step and/or the dispersing step is carried out under apressure of at most 1 MPa.

39. The method for producing an aqueous resin dispersion, wherein the50% particle diameter of the aqueous resin dispersion is at most 0.2 μm.

40. A method for producing an aqueous resin dispersion, which is amethod for producing an aqueous resin dispersion comprising a modifiedpolyolefin and water, and which comprises a dispersing step of adding,to a solution having a modified polyolefin dissolved in a solvent (a1)wherein the solubility of water at 20° C. is less than 1.0 wt %, waterand a solvent (a2) wherein the solubility of water at 20° C. is at least1.0 wt %, followed by dispersing, and a distillation step of distillingoff at least the solvents (a1) and (a2).

41. The method for producing an aqueous resin dispersion, wherein thesolvent (a1) is a hydrocarbon solvent which may be halogenated.

42. The method for producing an aqueous resin dispersion, wherein thesolvent (a2) has a boiling point lower than water.

43. The method for producing an aqueous resin dispersion, wherein thedispersing step is carried out under a pressure of at most 1 MPa.

44. The method for producing an aqueous resin dispersion, wherein at thetime of carrying out the distillation step, the compositional fractionof the solvent (a1) is smaller than the compositional fraction of thesolvent (a1) at the azeotropic point of the solvent (a1), the solvent(a2) and water.

45. The method for producing an aqueous resin dispersion, wherein the50% particle diameter of the aqueous resin dispersion is at most 0.2 μm.

46. The method for producing an aqueous resin dispersion, wherein amodifying step of subjecting a polyolefin to a modifying reaction toobtain the modified polyolefin, is carried out in the solvent (a1)thereby to obtain a solution having the modified polyolefin dissolved inthe solvent (a1).

47. The method for producing an aqueous resin dispersion, wherein apolymerization step of obtaining the polyolefin by a polymerizationreaction of a monomer, is further carried out in the solvent (a1).

48. The method for producing an aqueous resin dispersion, which includesa washing step of washing the solution with a solvent (a3) having asolubility in the solvent (a1) at 20° C. of less than 1.0 wt %.

49. A method for producing a modified polyolefin solution, whichcomprises carrying out a modifying step of subjecting a polyolefin to amodifying reaction in a solvent to obtain a solution containing amodified polyolefin and then a washing step of washing the solution witha solvent having a solubility in said solvent at 20° C. of less than 1.0wt %.

50. The method for producing a modified polyolefin solution, wherein themodifying step is a step of subjecting the polyolefin to a modifyingreaction in a hydrocarbon solvent which may be halogenated, to obtain asolution containing a modified polyolefin, and the washing step is astep of washing the solution with water.

51. The method for producing a modified polyolefin solution whereinafter the washing step, a dehydration is step is carried out.

52. The method for producing a modified polyolefin solution, wherein themodifying step is a step of reacting a polyolefin with a dicarboxylicanhydride to obtain a solution containing a polyolefin having adicarboxylic anhydride group bonded thereto.

53. The method for producing a modified polyolefin solution, whereinafter the washing step, a dehydration step is carried out and then, asecond modifying step of reacting the polyolefin having a dicarboxylicanhydride group bonded thereto, with a hydrophilic polymer, in thesolution, to obtain a solution containing a polyolefin having ahydrophilic polymer bonded thereto, is carried out.

Effects of the Invention

According to the present invention, in each of the first to fourthembodiments, the following effects (1) to (4) are obtainable. In thepresent invention, it is not required that all of such effects beobtained, and it is acceptable that at least one of such effects beobtainable.

(1) The aqueous dispersion is useful also for an application wherein anorganic solvent solution has heretofore been used for coating, suchbeing desirable also from the viewpoint of safety and health. Further,as it is not an organic solvent solution, discharge of VOC (volatileorganic compounds) can be reduced, such being desirable from theenvironmental viewpoint. Yet, it is possible to obtain an aqueousdispersion having excellent properties, which contains substantially nochlorine. As no chlorine is contained, there will be no problem ofdioxin or toxicity, such being very desirable from the environmentalviewpoint.

(2) A coated film obtained by applying a coating material containing theresin dispersion of the present invention is excellent in waterresistance, moisture resistance, oil resistance (GH resistance) andchemical resistance. Therefore, it is suitable also for a coating methodfor finishing by application of coating only once, such as a solventtype lacquer coating material. The resulting coated film exhibits goodadhesion to a polyolefin substrate, particularly to a propylene polymersubstrate, or to a plastic substrate containing e.g. a propylene polymermaterial, and it can be formed also on a hardly adhesive substrate suchas non-treated polypropylene, which is usually difficult to bond orapply coating.

(3) The resin dispersion obtainable by the present invention is veryuseful as a surface treating agent, an adhesive, a coating agent, acoating material, etc., for an olefin polymer having crystallinity.

(4) The laminate of the present invention is excellent in the coatedfilm adhesion and applicable to a wide range of industrial products.

Further, according to the first to fourth embodiments of the presentinvention, the following effects are respectively obtainable.

According to the first embodiment of the present invention, the polymer(C) is excellent in dispersibility in water and thus has a merit suchthat the dispersed particles have fine particle sizes and can bedispersed stably. Further, the polymer can be dispersed withsubstantially no addition of a surfactant, and there is a merit suchthat bleeding out of a surfactant, which used to be a problem, can beavoided, and a coated product having an excellent appearance can beobtained. Further, according to the method for producing a resindispersion of the present invention, it is possible to simply obtain anexcellent aqueous resin dispersion wherein the dispersed particle sizesare fine, and the resin particles are dispersed stably.

Further, when the polymer (C) of the present invention is used incombination with another resin to form a composite aqueous resindispersion, it is possible to improve the physical property valuesderived from such another resin, specifically to improve the strength,water resistance, weather resistance, abrasion resistance, solventresistance, etc. of the coated film.

According to the second embodiment of the present invention, thispolymer (IC) is excellent in dispersibility in water, whereby an aqueousresin dispersion excellent in stability with fine dispersed particlesizes can be obtained by an addition of a small amount of a surfactantor without adding any surfactant. Accordingly, a composite aqueous resindispersion comprising the polymer (IC) and the resin (ID) has a meritsuch that it is thereby possible to avoid bleeding out of a surfactantwhich used to be a problem, and it is possible to obtain a coatedproduct having an excellent appearance.

Further, the particle diameter of particles of the polymer (IC) is smallat a level of at most 0.9 time of the particle diameter of particles ofthe resin (ID), and when a coated film is formed, spaces among theparticles of the resin (ID) are filled with the particles of the polymer(IC), whereby the volume of spaces tends to be small, and there will bea merit such that the adhesion to the substrate will be high, and thewater resistance and the solvent resistance will be improved. Further,in the coated film, a sea-islands structure is formed wherein thepropylene polymer having a high adhesion to a propylene polymersubstrate constitutes “sea”, and other binder resins providing otherfunctions to the coated film constitutes “islands”, whereby there willbe a merit such that the adhesion to a substrate will be higher, and thewater resistance and the solvent resistance will be improved.

Further, according to the method for producing the resin dispersion ofthe present invention, it is possible to simply produce an excellentaqueous resin dispersion wherein the dispersed particle sizes are fine,the particle size distribution is narrow, and the resin particles aredispersed stably.

Further, as the composite aqueous resin dispersion contains the resin(ID) together with the polymer (IC), it is possible to improve thephysical property values derived from the resin (ID), specifically toimprove the strength, water resistance, weather resistance, abrasionresistance, solvent resistance, etc., of the coated film.

By the method for producing an aqueous resin dispersion according to thethird embodiment of the present invention, it is possible to simplyobtain an excellent aqueous resin dispersion wherein the dispersedparticle sizes are fine, the particle size distribution is narrow andthe resin particles are dispersed stably. Further, such dispersion canbe done substantially without adding or with an addition of a very smallamount of a surfactant, whereby there is a merit such that it ispossible to avoid bleeding out of a surfactant which used to be aproblem, and when the dispersion is used as a coating material, it ispossible to obtain a coated product having an excellent appearance.

Further, the solvent used for dispersion can easily be recovered, sinceit is readily separable from water after the distillation, such beingadvantageous in either reuse or disposal of the solvent.

By the method for producing an aqueous resin dispersion according to thefourth embodiment of the present invention, it is possible to simplyobtain an excellent aqueous resin dispersion wherein the dispersedparticle sizes are fine, the particle size distribution is narrow andthe resin particles are dispersed stably. Further, such dispersion canbe done substantially without adding or with an addition of a smallamount of a surfactant, whereby there is a merit such that it ispossible to avoid bleeding out of a surfactant which used to be aproblem, and when the dispersion is used as a coating material, it ispossible to obtain a coated product having an excellent appearance.

Further, as the solvent (a1) of the present invention, a solvent used ine.g. a step of modifying a polyolefin may be used as it is, wherebyafter completion of the previous step, the next dispersion process canbe carried out with the solution as dissolved in the solvent withoutnecessity to once remove or evaporate to dryness the solvent. Thus, theproduction process can be substantially simplified, thus providing avery useful production method.

BEST MODE FOR CARRYING OUT THE INVENTION

Now, the first to fourth embodiments of the present invention will,respectively, be described. However, descriptions common to therespective embodiments may sometimes be omitted, but it should beunderstood that descriptions with respect to the respective embodimentsmay be similarly applicable to other embodiments.

With Respect to the First Embodiment

The resin dispersion of the present invention is one having dispersed inwater a polymer (C) having a hydrophilic polymer (B) bonded to apolyolefin (A) in a ratio of (A):(B)=100:5 to 100:500 (weight ratio).Namely, the hydrophilic polymer is bonded in a predetermined ratio tothe polyolefin, and the obtained product is dispersed in water, wherebya resin dispersion having excellent characteristics can be obtained.

In the present invention, the dispersion is a concept including a statewherein dispersed particles are very small and dispersed in aunimolecular state, i.e. a state which can be said to be substantiallydissolution. Accordingly, there is no particular limit with respect tothe lower limit value for the dispersed particle size.

The ratio of the polyolefin (A) to the hydrophilic polymer (B) is(A):(B)=100:5 to 100:500 (weight ratio). As the ratio of the hydrophilicpolymer (B) becomes large, the polymer (C) tends to be well dispersed inwater, and the dispersed particle sizes tend to be small, whereby theparticles will be dispersed stably. For this purpose, the ratio of (B)is made larger than (A):(B)=100:5. On the other hand, as the ratio ofthe hydrophilic polymer (B) becomes small, the adhesion to a polyolefinsubstrate increases. For this purpose, the ratio of (B) is made smallerthan (A):(B)=100:500.

The method for producing the polymer (C) by bonding the hydrophilicpolymer (B) to the polyolefin (A), may usually be a method (R1) whereina hydrophilic monomer is polymerized in the presence of the polyolefin(A) to form the hydrophilic polymer (B) bonded to the polyolefin (A), ora method (R2) wherein a preliminarily polymerized hydrophilic polymer(B) is bonded to the polyolefin (A). Either method may suitably beselected for use depending upon the types and combination of thepolyolefin and the hydrophilic polymer, the desired properties of thepolymer (C), etc. Further, as the polyolefin (A) a polyolefin (A1)having no reactive group or a polyolefin (A2) having reactive groups maybe used.

Now, the respective cases will be described.

(1) Polyolefin (A)

As the polyolefin (A) of the present invention, a polyolefin (A1) havingno reactive group or a polyolefin (A2) having reactive groups may beused.

(1-1) Polyolefin (A1) Having No Reactive Group

As the polyolefin (A1), known various polyolefins and modifiedpolyolefins may be used. It is not particularly limited, and it may, forexample, be a homopolymer of ethylene or propylene, a copolymer ofethylene and propylene, or a copolymer of ethylene or/and propylene withanother comonomer. A comonomer may, for example, be an α-olefincomonomer having at least two carbon atoms, such as 1-butene, 1-pentene,1-hexene, 1-heptene, 1-octene, cyclopentene, cyclohexane or norbornene.The α-olefin comonomer is preferably a C₂₋₈ α-olefin comonomer, morepreferably a C₂₋₆ α-olefin comonomer. Or, a copolymer of at least twotypes of such α-olefin comonomers may also be used.

Further, a copolymer of an α-olefin monomer with a comonomer such asvinyl acetate, an acrylic acid ester or a methacrylic acid ester, or ahydrogenated product of at least two types of monomers selected fromaromatic vinyl monomers and conjugated diene monomers, may, for example,be used. Here, when the term “copolymer” is simply mentioned, it may bea random copolymer or a block copolymer. Further, the polyolefin (A1)may be straight-chained or branched.

Further, chlorinated polyolefins having such polyolefins chlorinated mayalso be used. The chlorination degree of such a chlorinated polyolefinis usually at least 5 wt %, preferably at least 10 wt %, and thechlorination degree is usually at most 50 wt %, preferably at most 30 wt%. However, for the purpose of reducing the environmental load, it ispreferred that the polyolefin (A1) contains substantially no chlorine.Here, “contains substantially no chlorine” means, for example, that thechlorination degree of the polyolefin is less than 5 wt %.

Specifically, the polyolefin (A1) may, for example, be a polyethylene, apolypropylene, an ethylene-propylene copolymer, a propylene-butenecopolymer, a propylene-hexene copolymer, a chlorinated polyethylene, achlorinated polypropylene, a chlorinated ethylene-propylene copolymer, achlorinated propylene-butene copolymer, an ethylene-vinyl acetatecopolymer, a hydrogenated product (SEBS) of styrene-butadiene-styreneblock copolymer (SBS) or a hydrogenated product (SEPS) ofstyrene-isoprene-styrene block copolymer (SIS). Preferred is a propylenehomopolymer or a copolymer of propylene with another α-olefin, which maybe chlorinated. More preferred is a propylene homopolymer, anethylene-propylene copolymer, a propylene-butene copolymer, achlorinated polypropylene, a chlorinated ethylene-propylene copolymer ora chlorinated propylene-butene copolymer. Further preferred is apropylene homopolymer, an ethylene-propylene copolymer or apropylene-butene copolymer.

The polyolefin (A1) preferably has a weight average molecular weight Mwof from 1,000 to 500,000, as measured by GPC (Gel PermeationChromatography) and calculated by a calibration curve of eachpolyolefin. The lower limit value is more preferably 10,000, furtherpreferably 30,000, particularly preferably 50,000. The upper limit valueis more preferably 300,000, further preferably 250,000, particularlypreferably 200,000. As Mw becomes higher than the lower limit value,stickiness tends to be less, and the adhesion to the substrate tends toincrease, and as it becomes lower than the upper limit value, theviscosity tends to be low, whereby the preparation of the resindispersion tends to be easy. Here, the GPC measurement is carried out bya conventional method employing a commercially available apparatus andby using e.g. o-dichlorobenzene as a solvent.

Of the polyolefin (A1), the molecular weight distribution Mw/Mnrepresented by the ratio of the weight average molecular weight Mw tothe number average molecular weight Mn, is preferably at most 10, morepreferably at most 5, further preferably at most 3. This means that themolecular weight distribution is narrow, and the molecular weight of thepolyolefin is uniform. By using such a polyolefin (A1), it becomes easyto control the particle size at the time of dispersion in water, andthere will be a merit such that a resin dispersion wherein the dispersedparticle sizes are small, the particle size distribution is narrow andthe particles are dispersed stably, can be obtained. Preferably, Mw/Mnis at most 3.0. However, it is usually at least 1.0.

The polyolefin (A1) preferably has a melting point Tm of at most 120°C., more preferably at most 110° C., further preferably at most 100° C.It is preferred that the melting point Tm is lower than 120° C., wherebythe crystallinity tends to be low, the solubility in the solvent will beimproved, and emulsification and dispersion operations tend to be morereadily carried out at a low temperature. However, the melting point Tmof the polyolefin (A1) is usually at least 25° C., preferably at least35° C. Such being advantageous from the viewpoint of high thermalresistance, high hardness and non-tackiness.

The content of propylene in the polyolefin (A1) is preferably at least50 mol %, more preferably at least 70 mol %. Usually, as the propylenecontent becomes high, the adhesion to a polypropylene substrate tends toincrease.

A preferred example of the polyolefin (A1) is one having entirely orpartially an isotactic structure as the stereoregularity of a propylenehomopolymer or copolymer. For example, not only a usually isotacticpolypropylene but also an isotactic block polypropylene or astereo-block polypropylene having isotactic blocks and atactic blocks,as disclosed in JP-A-2003-231714 (US2004-162403) or U.S. Pat. No.4,522,982, may, for example, be preferably used.

Further, in a case where the polyolefin (A1) is a propylene homopolymer,the “mmmm” pentad showing the isotactic stereoregularity is within arange of from 10% to 90%. The lower limit value is preferably 20%, morepreferably 30%, further preferably 40%. The upper limit value ispreferably 80%, more preferably 70%, further preferably 60%, stillfurther preferably 55%. As a method for measuring the ratio of thepentad, the method disclosed in JP-A-2003-231714 (US2004-162403) may beemployed. As the pentad ratio is higher than the lower limit value, thestickiness tends to be small, and as it is lower than the upper limitvalue, the crystallinity tends to be low, whereby the preparation of theliquid dispersion tends to be easy.

However, in a case where the polyolefin (A1) is a copolymer, even whenthe apparent stereoregularity is higher, for example, even when theabove “mmmm” pentad ratio is larger, it may preferably be used.

Or, another preferred example of the polyolefin (A1) is apropylene-α-olefin copolymer. Such a copolymer has a low melting pointas compared with a homopolymer such as polypropylene and thus has amerit such that with a resin dispersion employing such a copolymer, thebaking temperature after coating can be lowered. More preferably, thepropylene content is from 50 mol % to 95 mol %. Usually, as thepropylene content is high, the adhesion to a polypropylene substratetends to increase. It is preferably at least 60 mol %, more preferablyat least 70 mol %. However, the propylene content is at most 95 mol %.Usually, by lowering the propylene content, the melting point of thecopolymer can be lowered, and for example, there will be a merit suchthat the baking temperature after coating can be lowered. It ispreferably at most 90 mol %, more preferably at most 85 mol %. Further,the molecular weight distribution Mw/Mn of the copolymer is preferablyat most 3.0.

The α-olefin is preferably a C₂₋₆ α-olefin, more preferably a C₂₋₆α-olefin, further preferably a C₂₋₄ α-olefin, most preferably 1-butene.The 1-butene content is preferably from 5 mol % to 50 mol %. It is morepreferably at least 10 mol %, further preferably at least 15 mol %, andit is more preferably at most 40 mol %, further preferably at most 30mol %. Here, the copolymer may contain a small amount of constitutingunits derived from an α-olefin other than propylene and 1-butene. Forexample, it may contain at most 10 mol % of ethylene. More preferably,the ethylene content is at most 5 mol %. In this specification, butenemeans 1-butene unless otherwise specified.

As a commercial product available as the copolymer, Tafiner XM-7070 orXM-7080, manufactured by Mitsui Chemicals, Inc., may, for example, bementioned.

As the polyolefin (A1), one type may be used alone, or two or more typesmay be used in combination.

To sum up the foregoing, preferred as the polyolefin (A1) is apolyolefin wherein the propylene content is at least 50 mol % and is astereo-block polypropylene polymer having isotactic blocks and atacticblocks, a propylene-α-olefin copolymer, or a combination thereof.

The method for preparing the polyolefin (A1) of the present invention isnot particularly limited and may be any method so long as it is capableof producing a polymer satisfying the requirements of the presentinvention. For example, radical polymerization, cationic polymerization,anionic polymerization or coordination polymerization may be mentioned,and each may be living polymerization.

In the case of coordination polymerization, a method for polymerizationby a Ziegler Natta catalyst or a method for polymerization by a singlesite catalyst or a Kaminsky catalyst may, for example, be mentioned. Asa preferred method, a production method by means of a single sitecatalyst may be mentioned. Namely, in general, with a single sitecatalyst, by designing the ligand, the reaction can easily be controlledprecisely, whereby a polymer having a sharp molecular weightdistribution or stereoregularity distribution can be obtained, and ascompared with a polymer obtainable by a Ziegler Natta catalyst, themelting point is low, and with a resin dispersion employing such apolymer, it is possible to lower the baking temperature after thecoating. As the single site catalyst, a metallocene catalyst or aBrookhart type catalyst may, for example, be used. In the case of themetallocene catalyst, a preferred catalyst may be selected dependingupon the stereoregularity of the polyolefin to be polymerized, such asC₁ symmetric type, C₂ symmetric type, C_(2V) symmetric type or C_(s)symmetric type. Preferably, a C₁ symmetric type or C₂ symmetric typemetallocene catalyst may be employed.

Further, the polymerization may be of any type such as solutionpolymerization, slurry polymerization, bulk polymerization or gas-phasepolymerization. In the case of solution polymerization or slurrypolymerization, the solvent may, for example, be an aromatic hydrocarbonsuch as toluene or xylene; an aliphatic hydrocarbon such as hexane,octane or decane; an alicyclic aliphatic hydrocarbon such as cyclohexaneor methyl cyclohexane; a halogenated hydrocarbon such as methylenechloride, carbon tetrachloride or chlorobenzene; an ester such as methylacetate, ethyl acetate, propyl acetate or butyl acetate; a ketone suchas acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone; an alcohol such as methanol, ethanol, n-propanol,isopropanol or n-butanol; an ether such as dibutyl ether ortetrahydrofuran; or a polar solvent such as dimethylformamide ordimethylsulfoxide. Among them, an aromatic hydrocarbon, an aliphatichydrocarbon or an alicyclic hydrocarbon is preferred, and more preferredis toluene, xylene, hexane, heptane, cyclopentane or cyclohexane. Thesesolvents may be used alone or in combination as a mixture of two or moreof them.

(1-2) Polyolefin (A2) Having Reactive Groups

As the polyolefin (A2) having reactive groups, it is possible to employ,for example, a copolymer (A2a) obtained by copolymerizing an unsaturatedcompound having no reactive group with an unsaturated compound having areactive group at the time of polymerization of a polyolefin, or apolymer (A2b) obtained by graft-polymerizing a radical polymerizableunsaturated compound having a reactive group to a polyolefin, or apolymer (A2c) obtained by converting a polyolefin having unsaturatedterminal groups to one having groups of an element of Group 13 to 17.

The reactive groups may, for example, be carboxylic acid groups,dicarboxylic anhydride groups, dicarboxylic anhydride monoester groups,hydroxyl groups, amino groups, epoxy groups or isocyanate groups. Morepreferably, the polyolefin (A2) has at least one member selected fromthe group consisting of carboxylic acid groups, dicarboxylic anhydridegroups and dicarboxylic anhydride monoester groups. These carboxylicacid groups, etc. are highly reactive and can easily be bonded to ahydrophilic polymer. Not only that, there are many unsaturated compoundshaving such groups, which may easily be copolymerized orgraft-polymerized to a polyolefin.

The copolymer (A2a) is a copolymer which is obtainable by copolymerizingan unsaturated compound having no reactive group with an unsaturatedcompound having a reactive group and which has the unsaturated compoundhaving the reactive group inserted to the main chain. For example, it isobtainable by copolymerizing an α-olefin such as ethylene, propylene orbutene with an α,β-unsaturated carboxylic acid or its anhydride such asan acrylic acid or maleic anhydride. Specifically, as the copolymer(A2a), a propylene-butene-maleic anhydride copolymer may, for example,be used. Such polymers may be used alone or in combination as a mixtureof two or more of them. As the production method, a method described in(1-1) may be used in the same manner.

The polymer (A2b) is obtainable by graft-polymerizing a radicalpolymerizable unsaturated compound having a reactive group to apreliminarily polymerized polyolefin, wherein the unsaturated compoundhaving a reactive group is grafted to the main chain. It is for examplea polymer obtained by grafting (meth)acrylic acid, fumaric acid, maleicacid or its anhydride, itaconic acid or its anhydride, crotonic acid,2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate,(meth)acrylamino, (dimethylamino)ethyl (meth)acrylate, glycidyl(meth)acrylate, or (2-isocyanate)ethyl (meth)acrylate, to a polyolefinsuch as a polyethylene or a polypropylene. Such polymers may be usedalone or in combination as a mixture of two or more of them. Here,(meth)acrylic acid is a general term for acrylic acid and methacrylicacid, and such applies to other similar cases. As the polyolefin forthis reaction, the above-mentioned polyolefin having no reactive groupmay be used.

Specifically, the polymer (A2b) may, for example, be a maleicanhydride-modified polypropylene or its chlorinated product, a maleicanhydride-modified propylene-ethylene copolymer or its chlorinatedproduct, a maleic anhydride-modified propylene-butene copolymer or itschlorinated product, an acrylic acid-modified propylene or itschlorinated product, an acrylic acid-modified propylene-ethylenecopolymer or its chlorinated product, or an acrylic acid-modifiedpropylene-butene copolymer or its chlorinated product. These polymersmay be used alone or in combination as a mixture of two or more of them.

The radical polymerization initiator to be used for the graftpolymerization may be suitably selected for use from usual radicalpolymerization initiators, and for example, an organic peroxide orazonitrile may be mentioned. As the organic peroxide, a peroxyketal suchas di(t-butylperoxy)cyclohexane, a hydroperoxide such as cumenehydroperoxide, a dialkyl peroxide such as di(t-butyl) peroxide, a diacylperoxide such as benzoyl peroxide, or a peroxyester such as t-butylperoxy isopropyl monocarbonate may be used. The azonitrile may, forexample, be azobisbutyronitrile or azobisisopropylnitrile. Among them,benzoyl peroxide or t-butyl peroxy isopropyl monocarbonate isparticularly preferred. These initiators may be used alone or incombination as a mixture of two or more of them.

The ratio of the radical polymerization initiator to the graft copolymerunits to be used is usually within a range of radical polymerizationinitiator:graft copolymer units=1:100 to 2:1 (molar ratio), preferablywithin a range of 1:20 to 1:1.

The process for producing the polymer (A2b) is not particularly limitedand may be any method so long as it is capable of producing a polymersatisfying the requirements of the present invention. For example, asolution modification method (a method of heating and stirring in asolution for the reaction) or a melt modification method (a method ofmelting, heating and stirring in the absence of a solvent, or a methodof heating and kneading by an extruder for the reaction) may bementioned.

As the solvent in the case of production in the solution, the solventmentioned in (1-1) may be used in the same manner.

The reaction temperature is usually at least 50° C., preferably within arange of from 80 to 300° C. More preferably, in the case of the solutionmodification is method, the temperature is within a range of from 80 to200° C., and in the case of the melt modification method, thetemperature is within a range of from 150 to 300° C. The reaction timeis usually from about 2 to 20 hours. The reaction time is usually fromabout 2 to 20 hours.

The polymer (A2c) is usually employed in the case of producing a blockcopolymer. For example, a polyolefin (A2c1) obtained by converting adouble bond portion of a polyolefin having a terminal double bond to aGroup 13 element group such as a boron group or an aluminum group, asdisclosed in JP-A-2001-288372 (US2003-055179), a polyolefin (A2c2)obtained by converting a double bond portion of a polyolefin having aterminal double bond to a halogen element, as disclosed inJP-A-2005-048172 (EP1645576A1), or a polyolefin (A2c3) obtained byconverting a double bond portion of a propylene polymer having aterminal double bond to a mercapto group, as disclosed inJP-A-2001-298140 (U.S. Pat. No. 6,451,901), may be used.

The method for producing a polyolefin having a double bond may, forexample, be a method of inducing α-hydrogen detachment during the olefinpolymerization, or a method of thermally decomposing a propylene polymerat a high temperature.

The method for converting the double bond portion to a boron group or analuminum group may, for example, be a method of reacting an organicboron compound or an organic aluminum compound to the double bond in asolvent.

The method for converting the double bond portion to a halogen elementmay, for example, be a method wherein the above-mentioned polyolefin(A2c1) having an organic boron group is reacted with a base and anaqueous hydrogen peroxide solution to convert it to a propylene polymerhaving a hydroxyl group, which is then reacted with a halogengroup-containing acid halide to convert it to a halogen group-containingester group.

The method for converting the double bond portion to a mercapto groupmay, for example, be a method of reacting thioacetic acid in thepresence of a radical initiator, followed by treatment with a base.

The method for producing the polymer (A2c) is not particularly limitedand may be any method so long as it is capable of producing a polymersatisfying the requirements of the present invention. However, a methodof heating and stirring in a solution for the reaction is preferablyemployed. As the solvent in the case of production in the solution, thesolvent mentioned in (1-1) may be used in the same manner.

The content of reactive groups in the polymer (A2a) or (A2b) havingreactive groups bonded thereto, is preferably within a range of from0.01 to 5 mmol per 1 g of the polyolefin i.e. from 0.01 to 5 mol/g. Thelower limit value is more preferably 0.05 mmol/g, further preferably 0.1mmol/g, particularly preferably 0.15 mmol/g. The upper limit value ismore preferably 1 mmol/g, further preferably 0.8 mmol/g, particularlypreferably 0.5 mmol/g.

The content of reactive groups in the polymer (A2c) having reactivegroups bonded thereto is usually at most one reactive group per onemolecule of the polymer i.e. at most 1/number average molecular weightMn (mol/g), in view of its production method, and it tends to be low ascompared with the copolymer (A2a) and (A2b). Accordingly, it ispreferably within a range of from 0.004 to 2 mmol/g per 1 g of thepolyolefin. The lower limit value is more preferably 0.005 mmol/g. Theupper limit value is more preferably 0.2 mmol/g.

As the content is higher than the lower limit value, the amount of thehydrophilic polymer (B) bonded increases, and the hydrophilicity of thepolymer (C2) increases, whereby the dispersed particle sizes tend to besmall. As it is lower than the upper limit value, the adhesion to acrystalline polyolefin as the substrate tends to increase. Here, adicarboxylic anhydride group may be regarded as containing twocarboxylic acid groups in the group, and 1 mol of a dicarboxylicanhydride is counted to be 2 mols of the reactive group.

Polyolefins (A2) may be used alone or in combination as a mixture of twoor more of them. Further, as the polyolefin (A2), any of (A2a), (A2b)and (A2c) may be used, but preferred is usually the polymer (A2b). Ithas a merit such that the amount of the hydrophilic polymer (B) to bebonded can easily be controlled.

In the present invention, as the polyolefin (A), both of the polyolefin(A1) having no reactive group and the polyolefin (A2) having reactivegroups may suitably by used depending upon the combination with thehydrophilic polymer (B) or the desired properties of the polymer (C).However, at least, it is preferred to contain the polyolefin (A2) havingreactive groups, in view of merits such that the amount of thehydrophilic polymer (B) to be bonded can easily be controlled, andvarious reactions may be employed for such bonding. Only the olefin (A2)having reactive groups may be used.

(2) Hydrophilic Polymer (B)

In the present invention, the hydrophilic polymer is such a polymer thatwhen it is dissolved in water at 25° C. at a concentration of 10 wt %,the insoluble content is at most 1 wt %. As the hydrophilic polymer (B),any polymer may be used without any particular restriction so long asthe effects of the present invention are not substantially impaired, andany of a synthetic polymer, a semi-synthetic polymer and a naturalpolymer may be employed. It may have reactive groups.

The synthetic polymer is not particularly limited, and for example, apoly(meth)acrylic resin, a polyether resin, a polyvinyl alcohol resin ora polyvinyl pyrrolidone resin may, for example, be used. The naturalpolymer is not particularly limited, and for example, a starch such ascorn starch, wheat starch, sweet potato starch, potato starch, tapiocastarch or rice starch, a seaweed such as dried layer, agar or sodiumalginate, a plant mucilage such as gum Arabic, tragacauth gum or konjac,an animal protein such as hide glue, casein or gelatin, or a fermentedmucilage such as pullulan or dextrin may, for example, be used. Thesemisynthetic polymer is not particularly limited, and for example, astarch such as carboxyl starch, cation starch or dextrin, or a cellulosesuch as viscose, methyl cellulose, ethyl cellulose, carboxylmethylcellulose or hydroxyethyl cellulose may, for example, be used.

Among them, preferred is a synthetic polymer whereby the degree ofhydrophilicity can easily be controlled, and the properties arestabilized. More preferred is an acrylic resin such as apoly(meth)acrylic resin, a polyvinyl alcohol resin, a polyvinylpyrrolidone resin or a polyether resin. They may be used alone or incombination as a mixture of two or more of them. A highly hydrophilicpolyether resin is most preferred.

The acrylic resin to be used in the present invention is usuallyobtained by polymerizing an unsaturated carboxylic acid or its ester oranhydride by radical polymerization, anionic polymerization or cationicpolymerization. The method for bonding it with the polyolefin (A) is notparticularly limited, and for example, a method of carrying out radicalpolymerization in the presence of a polyolefin, or a method of reactingan acrylic resin having a reactive group such as a hydroxyl group, anamino group, a glycidyl group or a carboxylic (anhydride) group with apolyolefin having a reactive group, may, for example, be mentioned.

The hydrophilic unsaturated carboxylic acid or its ester or anhydridemay preferably be (meth)acrylic acid, hydroxylethyl (meth)acrylate,dimethylaminoethyl (meth)acrylate, a quaternary product ofdimethylaminoethyl (meth)acrylate or (meth) acrylamide.

Further, within a range wherein hydrophilicity is shown, a hydrophobicradical polymerizable compound (a hydrophobic monomer) may becopolymerized thereto. A copolymerizable hydrophobic monomer may, forexample, be a (meth)acrylic acid ester monomer having a C₁₋₁₂ alkyl,aryl or arylalkyl group, or a polymerizable vinyl monomer having a C₁₋₁₂hydrocarbon group.

The (meth)acrylic acid ester monomer having a C₁₋₁₂ alkyl group may, forexample, be methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl(meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate,isobutyl (meth)acrylate, t-butyl (meth)acrylate, hexyl (meth)acrylate,cyclohexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl(meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate or dodecyl(meth)acrylate.

The (meth)acrylic acid ester monomer having a C₁₋₁₂ aryl or arylalkylgroup may, for example, be phenyl (meth)acrylate, toluoyl (meth)acrylateor benzyl (meth)acrylate.

The polymerizable vinyl monomer having a C₁₋₁₂ hydrocarbon group may,for example, be vinyl acetate or a styrene monomer.

Preferred may, for example, be a (meth)acrylic acid ester such as methyl(meth)acrylate or butyl (meth)acrylate, or vinyl acetate.

Otherwise, a radical polymerizable unsaturated compound may bepolymerized in the presence of a radical polymerization initiator toform a polymer and at the same time to bond it to the polyolefin (A),followed by modifying it to the hydrophilic polymer (B). For example, amethod wherein t-butyl (meth)acrylate is polymerized and then hydrolyzedunder an acidic condition to convert it to a poly(meth)acrylic acid, ora method wherein vinyl acetate is polymerized and then saponified tomodify it to a polyvinyl alcohol, may be mentioned. In such a case, asthe polyolefin (A), a polyolefin (A2) having reactive groups bondedthereto may be used, but usually, a polyolefin (A1) having no reactivegroup is employed.

The polyvinyl alcohol resin to be used in the present invention isobtained usually by polymerizing vinyl acetate to obtain a polyvinylacetate, followed by saponification. The saponification degree may becomplete saponification or partial saponification.

The polyvinyl pyrrolidone resin to be used in the present invention isobtained usually by polymerizing vinyl pyrrolidone.

The polyether resin to be used in the present invention is obtainedusually by subjecting a cyclic alkylene oxide or a cyclic alkylene imineto ring-opening polymerization. The method for bonding it to thepolyolefin (A) is not particularly limited, and for example, a method ofsubjecting a cyclic alkylene oxide to ring-opening polymerization in thepolyolefin (A2) having reactive groups, or a method of reacting ahydrophilic polymer having reactive groups such as a polyether polyol ora polyether amine obtained by e.g. ring-opening polymerization, with thepolyolefin (A2) having reactive groups, may, for example, be mentioned.

The polyether amine is a compound having a primary amino group as areactive group at one terminal or both terminals of a resin having apolyether skeleton. The polyether polyol is a compound having a hydroxylgroup as a reactive group at both terminals of a resin having apolyether skeleton.

The hydrophilic polyalkylene oxide or polyalkylene imine may preferablybe polyethylene oxide, polypropylene oxide, polypropylene oxide orpolyethylene imine.

Or, as the polyether amine, Jeffamine M series, D series or ED series,manufactured by Huntsman Corporation may, for example, be used.

Before bonding to the polyolefin (A), the hydrophilic polymer (B) to beused in the present invention preferably has at least one reactive groupwhich is reactive thereto. As such a reactive group, a carboxylic acidgroup, a dicarboxylic anhydride group, a dicarboxylic anhydridemonoester group, a hydroxyl group, an amino group, an epoxy group or anisocyanate group may, for example, be mentioned. Preferably, it has atleast an amino group. The amino group has a high reactivity with variousreactive groups such as a carboxylic acid group, a carboxylic anhydridegroup, a glycidyl group and an isocyanate group, whereby it is easy tobond the hydrophilic polymer to the polyolefin. The amino group may beprimary, secondary or tertiary, but more preferred is a primary aminogroup.

At least one reactive group may be present, but more preferably, it hasonly one reactive group. If it has two or more reactive groups, at thetime of bonding it to the polyolefin (A), it tends to form a threedimensional network structure and is likely to be geled.

However, it may have a plurality of reactive groups, if a reactive grouphaving a higher reactivity than others is only one. For example, ahydrophilic polymer is having a plurality of hydroxyl groups and oneamino group having a higher reactivity than the hydroxyl groups, is apreferred example. Here, the reactivity is a reactivity with thereactive group of the polyolefin (A).

The hydrophilic polymer (B) in the present invention is required to havea high molecular weight in order to impart sufficient hydrophilicity,and it is one having a weight average molecular weight Mw of at least200, as measured by GPC and calculated by a calibration curve ofpolystyrene. The lower limit value is preferably 300, more preferably500. However, the weight average molecular weight Mw is preferably atmost 200,000. The upper limit value is more preferably 100,000, furtherpreferably 10,000. As Mw is higher than the lower limit value, thehydrophilicity of the polymer (C) tends to increase, and the dispersedparticle sizes tend to be small so that the dispersion tends to bestabilized, and as it is lower than the upper limit value, the viscositytends to be low, and the preparation of the resin dispersion tends to beeasy. Here, the GPC measurement is carried out by a conventional methodusing a commercial available apparatus and by using e.g. THF as asolvent.

The amount of the hydrophilic polymer (B) bonded to the polyolefin (A)is preferably from 0.01 to 5 mmol per 1 g of the polyolefin (A), i.e.from 0.01 to 5 mmol/g. The lower limit value is more preferably 0.05mmol/g, further preferably 0.1 mmol/g, particularly preferably 0.15mmol/g. The upper limit value is more preferably 1 mmol/g, furtherpreferably 0.8 mmol/g, particularly preferably 0.5 mmol/g, mostpreferably 0.3 mmol/g. As the amount is higher than the lower limitvalue, the hydrophilicity of the polymer (C) tends to increase, and thedispersed particle sizes tend to be small so that the dispersion tendsto be stabilized, and as it is lower than the upper limit value, theadhesion to a crystalline polyolefin as a substrate tends to increase.

The polyolefin (A) and the hydrophilic polymer (B) may form a graftcopolymer having the hydrophilic polymer (B) graft-bonded to thepolyolefin (A), or a block copolymer of the polyolefin (A) and thehydrophilic polymer (B) including such a state that the hydrophilicpolymer (B) is bonded to one end or both ends of the polyolefin (A).However, preferred is a graft copolymer in view of such merits that thecontent of the hydrophilic polymer (B) is easy to control, and ascompared with a block copolymer, the content of the hydrophilic polymer(B) can easily be increased.

The hydrophilic polymer (B) may be bonded to the polyolefin (A) byvarious reaction modes. The reaction mode is not particularly limited,but it is, for example, a radical graft reaction or a reaction utilizingreactive groups.

By the radical graft reaction, a bond by a carbon-carbon covalent bondwill be formed.

The reaction utilizing reactive groups is one wherein both of thepolyolefin (A) and the hydrophilic polymer (B) have reactive groups, andthey are bonded by reacting the reactive groups, whereby a covalent bondor an ionic bond will be formed. Such a reaction may, for example, be a(ring-opening) esterification reaction of a carboxylic (anhydride) groupwith a hydroxyl group, a ring-opening reaction of a carboxylic acidgroup with an epoxy group, a ring-opening reaction of a primary orsecondary amino group with an epoxy group, a (ring-opening) amidationreaction or imidation reaction of a carboxylic (anhydride) group with aprimary or secondary amino group, a quaternary ammonium-forming reactionof a carboxylic acid group with a tertiary amino group, an amidationreaction of a carboxylic acid group with an isocyanate group, an ureareaction of a primary or secondary amino group with an isocyanate group,or an urethane reaction of a hydroxyl group with an isocyanate group.Among them, a ring-opening amidation reaction or imidation reaction of acarboxylic anhydride group with a primary or secondary amino group ispreferred from the viewpoint of the high reactivity. Further, theamidation is preferred to the imidation, since hydrophilic groups suchas a NH group and a COOH group will remain in the groups, whereby theemulsification will be easy. The reaction rate in each reaction mayoptionally be selected within a range of from 1 to 100%, preferably from50 to 100%, more preferably from 70 to 100%. In a case where acarboxylic acid group is a dibasic acid or its anhydride, against oneequivalent of the dibasic acid or its anhydride, one equivalent may bereacted, or two equivalents may be reacted.

(3) Polymer (C)

Usually, as a method for producing the polymer (C) by bonding thehydrophilic polymer (B) to the polyolefin (A), there is a method (R1)wherein a hydrophilic monomer is polymerized in the presence of thepolyolefin (A) to form the hydrophilic polymer (B) bonded to thepolyolefin (A), or a method (R2) wherein a preliminarily polymerizedhydrophilic polymer (B) is bonded to the polyolefin (A). In eithermethod, as the polyolefin (A), a polyolefin (A1) having no reactivegroup or a polyolefin (A2) having reactive groups may be used.

(3-1) Method (R1) for Producing Polymer (C)

In this method, a hydrophilic radical polymerizable unsaturated compound(hydrophilic monomer) is polymerized in the presence of a polyolefin toobtain a hydrophilic polymer (B) bonded to the polyolefin. The methodfor polymerization of the hydrophilic monomer may, for example, beaddition polymerization, condensation polymerization or ring-openingpolymerization. At that time, a hydrophobic radical polymerizableunsaturated compound (hydrophobic monomer) may be copolymerized within arange where a hydrophilic polymer can be formed. In any case, as thepolyolefin, a polyolefin (A1) having no reactive group, or a polyolefin(A2) having reactive groups bonded thereto, may be used.

Specifically, there is, for example, a method wherein a hydrophilicradical polymerizable unsaturated compound is graft-polymerized in thepresence of the polyolefin (A) and a radical-polymerization initiatorsuch as a peroxide or azo compound to obtain a graft copolymer of thepolyolefin and polyacryl. Further, as disclosed in JP-A-2001-288372(US2003-055179), there is a method wherein a hydrophilic radicalpolymerizable unsaturated compound is polymerized in the presence of apolyolefin (A2c1) having a Group 13 element group such as a boron groupor an aluminum group at its terminal to obtain a block copolymer of thepolyolefin and polyacryl. Further, as disclosed in JP-A-2004-131620(US2004-110903) or JP-A-2005-048172 (EP1645576A1), there is a methodwherein a block copolymer of a propylene polymer and a polyacryl isprepared by an atom transfer living radical method by using a polyolefin(A2c2) having a halogen atom at its terminal and a copper halide,ruthenium halide or the like. Further, as disclosed in JP-A-2001-098140(U.S. Pat. No. 6,451,901), there is a method wherein a radical initiatorand a hydrophilic radical polymerizable unsaturated compound arepolymerized in the presence of a polyolefin having a mercapto group atits terminal to obtain a block copolymer of the polyolefin andpolyacryl.

The hydrophilic monomer is not particularly limited, and for example,(meth)acrylic acid, hydroxyethyl (meth)acrylate, methoxypolyethyleneglycol (meth)acrylate, dimethylaminoethyl (meth)acrylate, quaternarydimethylaminoethyl (meth)acrylate or vinyl pyrrolidone may be mentioned.

As the copolymerizable hydrophobic monomer, one mentioned in (2) may beused in the same manner.

A reactive surfactant or a reactive emulsifier may also be used as anaqueous radical polymerizable unsaturated compound. For example, analkyl propenylphenol polyethylene oxide adduct, an alkyldipropenylphenolpolyethylene oxide adduct and their sulfuric acid ester salts asdisclosed in JP-A-04-053802 (U.S. Pat. No. 5,332,854) and JP-A-04-050204(U.S. Pat. No. 5,324,862) may be mentioned. Among them, analkylpropenylphenol ethylene oxide 20 mol adduct, 30 mol adduct or 50mol adduct (Aqualon RN-20, RN-30 or RN-50, manufactured by Daiichi KogyoSeiyaku Co., Ltd.), or a sulfuric acid ester ammonium salt of analkylpropenylphenol polyethylene oxide 10 mol adduct, or a sulfuric acidester ammonium salt of the same 20 mol adduct (Aqualon HS-10 or HS-20,manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is used preferably.

Otherwise, a radical polymerizable unsaturated compound may bepolymerized in the presence of a radical polymerization initiator toform a polymer and at the same time to bond it to a polyolefin, andthen, the hydrophilic polymer (B) may be modified. For example, a methodwherein t-butyl (meth)acrylate is polymerized and then hydrolyzed in thepresence of an acid to modify it to a poly(meth)acrylic acid, or amethod of further neutralizing it with a base, or a method wherein vinylacetate is polymerized and then saponified to modify it to a polyvinylalcohol, may be mentioned. As a copolymerizable hydrophobic radicalpolymerizable unsaturated compound, a (meth)acrylic acid ester such asmethyl (meth)acrylate or butyl (meth)acrylate, or vinyl acetate may bementioned. In such a case, as the polyolefin (A), a polyolefin (A2)having reactive groups bonded thereto may be used, but usually, apolyolefin (A1) having no reactive group is employed.

Or, there is a method wherein a polyolefin (A2) having reactive groupsis employed, and using such reactive groups as initial terminals, ahydrophilic ring-opening polymerization monomer or the like ispolymerized to obtain a hydrophilic polymer (B).

The hydrophilic ring-opening polymerization monomer may, for example, beethylene oxide, propylene oxide or ethylene imine. The copolymerizablehydrophobic monomer may, for example, be trimethylene oxide,tetrahydrofuran, β-propiolactone, γ-butyrolactone or ε-caprolactone.

They may be used alone or in combination as a mixture of two or more ofthem.

The reaction method is not particularly limited so long as a polymersatisfying the requirements of the present invention can thereby beproduced. For example, a method of heating and stirring in a solutionfor the reaction, a method of melting, heating and stirring in theabsence of a solvent for the reaction, or a method of heating andkneading by an extruder for the reaction, may be mentioned. The reactiontemperature is usually within a range of from 0 to 200° C., preferablywithin a range of from 30 to 150° C. As the solvent in the case ofproduction in a solution, the solvent mentioned in (1-1) may be used inthe same manner.

(3-2) Method (R2) for Producing Polymer (C)

In this method, a preliminarily polymerized hydrophilic polymer (B) isbonded to the polyolefin (A). In this case, as the hydrophilic polymer(B), one mentioned in (2) may be used.

Specifically, there is, for example, a method wherein firstly, at thetime of polymerizing a hydrophilic monomer to form a hydrophilicpolymer, an unsaturated double bond is retained in its molecule, andthen it is graft-polymerized to the polyolefin (A) by means of a radicalpolymerization initiator. In such a case, as the polyolefin (A), apolyolefin (A2) having reactive groups may be used, but usually, apolyolefin (A1) having no reactive group is used.

Further, there is a method wherein firstly, a hydrophilic polymer havinga reactive group at its terminal is formed by polymerization, and thenthis is bonded to a polyolefin (A2) having reactive groups. Thehydrophilic polymer having a reactive group at its terminal may beobtained by polymerizing a hydrophilic monomer by using a compoundhaving a reactive group, as an initiator or a chain transfer agent. Or,it may be obtained by ring-opening polymerization of a hydrophilicring-opening polymerization monomer such as an epoxy compound.

As the hydrophilic monomer which may be used in such a case, varioushydrophilic monomers mentioned in (3-1) may be used in the same manner.

They may be used alone or in combination as a mixture of two or more ofthem.

The reaction method is not particularly limited and may be any method solong as a polymer satisfying the requirements of the present inventioncan thereby be produced. For example, a method of heating and stirringin a solution for the reaction, a method of melting, heating andstirring in the absence of a solvent for the reaction, or a method ofheating and kneading by an extruder for the reaction, may be mentioned.The reaction temperature is usually within a range of from 0 to 200° C.,preferably within a range of from 30 to 150° C. As the solvent in thecase of production in a solution, the solvent mentioned in (1-1) may beused in the same manner.

(4) Method for Producing Aqueous Resin Dispersion

The method for producing a resin dispersion of the present invention isnot particularly limited, and for example, a method which comprisespreparing a mixture of the polymer (C), water and a solvent other thanwater, and then, removing the solvent from the mixture to obtain anaqueous dispersion, or a method which comprises melting the polymer (C)at a temperature of at least the melting temperature of the polymer (C),and then, adding water thereto to obtain a dispersion, may be mentioned.

Preferred is the former. By the method which comprises preparing amixture of the polymer, water and a solvent other than water, and then,removing the solvent from the mixture to obtain an aqueous dispersion,an aqueous dispersion with fine particle sizes can easily be prepared.At the time of preparing the mixture, heating may be applied as the caserequires. The temperature is usually from 30 to 150° C. The proportionof the solvent other than water in the resin dispersion is made to beusually at most 50%, finally. It is preferably at most 20%, morepreferably at most 10%, particularly preferably at most 1%.

More preferred is a method wherein the solvent other than water is addedto the polymer (C), and after dissolving it, if necessary, by heating,water is added, whereby an aqueous dispersion with finner particle sizescan easily be prepared. The temperature at the time of dissolving thepolymer in the solvent or at the time of adding water, is usually from30 to 150° C. In a case where the solvent is once dissolved in thesolvent other than water, the solvent may be distilled off after theaddition of water. The proportion of the solvent other than water in theresin dispersion is as described above.

The solvent other than water to be used in this method may, for example,be an aromatic hydrocarbon such as toluene or xylene; an aliphatichydrocarbon such as hexane, octane or decane; an alicyclic aliphatichydrocarbon such as cyclohexane or methyl cyclohexane; a halogenatedhydrocarbon such as methylene chloride, carbon tetrachloride orchlorobenzene; an ester such as methyl acetate, ethyl acetate, propylacetate or butyl acetate; a ketone such as acetone, methyl ethyl ketone,methyl propyl ketone, methyl isobutyl ketone or cyclohexanone; analcohol such as methanol, ethanol, n-propanol, isopropanol, n-butanol,2-butanol, isobutanol, t-butanol, cyclohexanol, ethylene glycol,propylene glycol or butanediol; an ether such as dipropyl ether, dibutylether or tetrahydrofuran; an organic solvent having two or morefunctional groups, such as 2-methoxyethanol, 2-ethoxyethanol,2-butoxyethanol, 2-methoxypropanol, 2-ethoxypropanol or diacetonealcohol; or a polar solvent such as dimethylformamide ordimethylsulfoxide.

Among them, a solvent soluble in water in an amount of at least 1 wt %is preferred, and more preferred is one soluble in water in an amount ofat least 5 wt %. For example, methyl ethyl ketone, methyl propyl ketone,cyclohexanone, n-propanol, isopropanol, n-butanol, 2-butanol,isobutanol, t-butanol, cyclohexanol, tetrahydrofuran, 2-methoxyethanol,2-ethoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-ethoxypropanol ordiacetone alcohol is preferred.

An example of a particularly preferred method for producing an aqueousresin dispersion of the present invention may be a production methodwhich comprises a dissolving step of dissolving the polymer (C) in asolvent (a) wherein the solubility of water at 20° C. is from 1.0 to95.0 wt %, and a dispersing step of adding water thereto, followed bydispersing, and a distillation step of distilling off at least thesolvent (a). This method will be described in detail in “WITH RESPECT TOTHE THIRD EMBODIMENT”.

Another example of a particularly preferred production method may be aproduction method which comprises a dispersing step of adding, to asolution having the polymer (C) dissolved in a solvent (a1) wherein thesolubility of water at 20° C. is less than 1.0 wt %, water and a solvent(a2) wherein the solubility of water at 20° C. is at least 1.0%,followed by dispersing, and a distillation step of distilling off atleast the solvents (a1) and (a2). This method will be described indetail in “WITH RESPECT TO THE FOURTH EMBODIMENT”.

An apparatus to produce the resin dispersion by adding water afterbringing the polymer in a state melted or dissolved in a solvent, is notparticularly limited, and for example, a reactor equipped with astirrer, or a single screw or twin screw kneader may be used. Thestirring speed at that time varies to some extent depending upon thechoice of the apparatus, but it is usually within a range of from 10 to1,000 rpm.

(5) Aqueous Resin Dispersion

The polymer (C) of the present invention is excellent in dispersibilityin water, and according to the method for producing a resin dispersionof the present invention, an aqueous resin dispersion with finedispersed particle sizes can be obtained. Therefore, the aqueous resindispersion of the present invention has merits such that the dispersedparticle sizes are fine, and the resin is dispersed stably. Accordingly,when it is used, a coated product having an excellent appearance can beobtained.

With respect to the dispersed particle sizes of the polymer (resin) inthe resin dispersion, when the particle diameter at 50% on cumulativebasis from the finest particle diameter as calculated by volume (whichis referred to as the 50% particle diameter, the 50% average particlediameter, the volume average particle diameter, or the median diameter)is obtained, the 50% particle diameter is usually at most 10 μm,preferably at most 1 μm. According to the present invention, the 50%particle diameter may be made to be at most 0.5 μm, more preferably atmost 0.3 μm, further preferably at most 0.2 μm, most preferably at most0.1 μm. When the 90% particle diameter is likewise obtained, morepreferably, the 90% particle diameter may be made to be at most 1 μm,particularly preferably at most 0.5 μm. By adjusting the dispersedparticle diameter to be small, it is possible to improve the dispersionstability, whereby agglomeration tends to hardly take place, and theparticles can be dispersed more stably. Further, the ratio of the 90%particle diameter to the 50% particle diameter being small means thatthe particle size distribution is narrow, and consequently, thedispersion stability is improved.

In the resin dispersion of the present invention, the solid content ispreferably at least 5 wt %, more preferably at least 10 wt %, furtherpreferably at least 20 wt %, based on the entirety. And, it ispreferably at most 70 wt %, more preferably at most 60 wt %, furtherpreferably at most 50 wt %, particularly preferably at most 40 wt %. Thesmaller the amount of the solid content, the lower the viscosity,whereby the dispersion can be applied to various coating methods and iseasy to use, and the stability as a dispersion tends to be high.However, for example, when it is used as a primer or an adhesive, thesolid content is preferably high in order to save the energy and timefor drying water after the coating.

As described in the foregoing, the aqueous resin dispersion of thepresent invention has merits such that no surfactant is required, andyet, the dispersed particle sizes are very fine.

However, a surfactant may be incorporated as the case requires dependingupon the application or other purposes.

As the surfactant, a cationic surfactant, an anionic surfactant, anonionic surfactant, an amphoteric surfactant or a reactive surfactantmay, for example, be used. As a surfactant, one having, as a hydrophobicgroup, an alkyl, alkenyl, alkylaryl or alkenylaryl group having at least4 carbon atoms, is usually employed. The carbon number is preferably atleast 8, more preferably at least 12. However, the carbon number isusually at most 30.

The nonionic surfactant may, for example, be polyoxyethylene cetylether, polyoxyethylene stearyl ether, polyoxyethylene nonyl phenyl etheror polyoxyethylene sorbitan monolaurate. The anionic surfactant may, forexample, be sodium dodecylbenzenesulfonate, sodium sulfosuccinate,sodium lauryl sulfate, or sodium polyoxyethylene lauryl sulfate. Thecationic surfactant may, for example, be stearyl trimethylammoniumchloride, or cetyl trimethylammonium bromide. The amphoteric surfactantmay, for example, be lauryl dimethylamino succinic acid betaine.

Further, as the above surfactant, a so-called reactive surfactant havinga radical polymerization functional group may, for example, be used.When such a reactive surfactant is used, the water resistance of thecoating film formed by using such a resin dispersion can be improved. Atypical commercially available reactive surfactant may, for example, beEleminol JS-2 (manufactured by Sanyo Chemical Industries, Ltd.) orLatemul S-180 (manufactured by Kao Corporation).

The amount of the surfactant per 100 parts by weight of the polymer (C)is usually at most 50 parts by weight, preferably at most 30 parts byweight.

However, no surfactant being required is one of merits of the presentinvention. Accordingly, the amount of the surfactant should better besmall, and the content of the surfactant in the resin dispersion ispreferably at most 10 parts by weight per 100 parts by weight of thepolymer (C). It is more preferably at most 5 parts by weight, furtherpreferably at most 2 parts by weight. The surfactant may notsubstantially be contained. The surfactant being not substantiallycontained means that the content is less than 1 part by weight per 100parts by weight of the polymer (C).

By reducing the amount of the surfactant, it is possible to preventbleeding out which used to be a problem, and there is a merit that acoated product having an excellent appearance can be obtained, and theresin dispersion of the present invention can be used as a coatingmaterial for the outermost surface of the coating. Further, if asurfactant is contained, the water resistance of the coating tends to below, and from this viewpoint, the amount of the surfactant should betterbe small.

However, a nonionic surfactant tends to hardly deteriorate the waterresistance as compared with other surfactants, and accordingly, anonionic surfactant may be contained in a relatively large amount. Forexample, in a case where surfactants other than a nonionic surfactantshould be at most 5 parts by weight per 100 parts by weight of thepolymer (C), the nonionic surfactant may be at most 10 parts by weight.

Further, it is also one of merits of the present invention that theamount of the surfactant can be reduced even without using a chlorinatedpolyolefin, whereby the environmental load can be reduced.

To the resin dispersion of the present invention, an acidic substance ora basic substance may be added as the case requires. As the acidicsubstance, an inorganic acid such as hydrochloric acid or sulfuric acid,or an organic acid such as acetic acid, may, for example, be mentioned.As the basic substance, an inorganic base such as sodium hydroxide orpotassium hydroxide, or an organic base such as ammonia, methylamine,ethylamine, propylamine, butylamine, hexylamine, octylamine,ethanolamine, propanolamine, diethanolamine, N-methyldiethanolamine,dimethylamine, diethylamine, triethylamine, tripropylamine,N,N-dimethylethanolamine, 2-dimethylamino-2-methyl-1-propanol,2-amino-2-methyl-1-propanol or morpholine, may, for example, bementioned.

It is preferred to add a basic substance in a case where the resin hasacidic groups and to add an acidic substance in a case when the resinhas basic groups, whereby there will be a merit that the hydrophilicityof the resin can be increased, and the dispersed particle sizes can bemade finner.

To the resin dispersion of the present invention, various additives maybe incorporated as the case requires within a range not to substantiallyimpair the effects of the present invention. For example, variousstabilizers such as an ultraviolet absorber, an antioxidant, a weatherresistant stabilizer or a heat resistant agent; colorants such astitanium oxide and an organic pigment; and various additives such aspigment, carbon black, an electroconductivity-imparting agent such asferrite, a dye, a pigment dispersant, a leveling agent, a defoamingagent, a thickener, an antiseptic, a mildewcide, an anti-corrosion agentand a wetting agent, may be incorporated.

The defoaming agent may, for example, be SURFYNOL 104PA or SURFYNOL 440manufactured by Air Products.

In order to further improve various coating film properties such aswater resistance and solvent resistance, a crosslinking agent may beadded in an amount of from 0.01 to 100 parts by weight per 100 parts byweight of the resin in the dispersion. As such a crosslinking agent, aself-crosslinkable crosslinking agent, a compound having a plurality offunctional groups reactive with carboxyl groups in its molecule, or ametal complex having polyvalent coordination positions, may, forexample, be used. Among them, an isocyanate compound, a melaminecompound, a urea compound, an epoxy compound, a carbodiimide compound,an oxazoline group-containing compound, a zirconium salt compound or asilane coupling agent may, for example, be preferred. Or, suchcrosslinking agents may be used in combination.

In a case where the resin dispersion of the present invention is to beused as a primer, coating material or ink, a hydrophilic organic solventother than water may be incorporated for the purpose of increasing thedrying speed or to obtain a good finished surface. Such a hydrophilicorganic solvent may, for example, be an alcohol such as methanol orethanol, a ketone such as acetone, a glycol such as ethylene glycol orpropylene is glycol, or its ether, or N-methylpyrrolidone. Preferred isisopropanol, ethanol, propylene glycol monomethyl ether, ethylene glycolmonobutyl ether or N-methylpyrrolidone. The content of such ahydrophilic organic solvent is usually at most 20 wt %, preferably atmost 10 wt %, more preferably at most 5 wt %, based on the total amountof water and the organic solvent.

(5-1) Combined Use of Other Resins

To the resin dispersion of the present invention, an aqueous resin or aresin dispersible in water may be mixed for use, as the case requires,within a range not to substantially impair the effects of the presentinvention. For example, such a combined use is effective for improvingthe coating exterior appearance (glazing or delustering) or to reducetackiness. It may be a resin dispersible by means of a surfactant. As anaqueous resin, a resin mentioned as a hydrophilic polymer (B) may, forexample, be used, and for example, an aqueous solution having such aresin dissolved in water may be mixed to the resin dispersion of thepresent invention.

The resin dispersible in water may, for example, be an acrylic resin, apolyepoxy resin, a polyester resin, a polyurethane resin, a melamineresin or an alkyd resin. The form of the resin dispersion containingsuch a resin and the polymer (C) is not particularly limited. Forexample, such a resin and the polymer (C) may, respectively, beemulsified and then mixed. By this method, particles made of such aresin and particles made of the polymer (C) are respectively separatelyformed, and an aqueous resin dispersion having the respective particlesdispersed in water is obtainable.

Or, there is a method wherein such a resin and the polymer (C) are mixedand then emulsified. By this method, an aqueous resin dispersion isobtainable wherein particles each made of a mixture of such a resin andthe polymer (C), are dispersed in water. For example, by permitting thepolymer (C) to be coexistent during the polymerization of such a resin,two of them can be mixed and emulsified and dispersed in water to formparticles each containing such a resin and the polymer (C). Otherwise,the resin and the polymer (C) may be separately synthesized, followed bye.g. melt-kneading to mix them, followed by emulsification anddispersion in water to form particles each containing the resin and thepolymer (C).

An aqueous resin dispersion wherein particles made of the polymer (C)and particles made of the resin are separately present, is preferred inorder to let the polymer (C) and the resin exhibit the respectiveproperties effectively. Such an aqueous resin dispersion may beobtained, for example, by mixing a dispersion having the polymer (C)emulsified and dispersed in water and a dispersion having the resinemulsified and dispersed in water.

The weight ratio of the polyolefin (A) to said another resin ispreferably from 90:10 to 10:90. Namely, based on 100 parts by weight ofthe total amount of the polyolefin component and another resin, theamount of the polyolefin (A) is preferably at least 10 parts by weightand at most 90 parts by weight. If the amount of the polyolefin (A) isless than 10 parts by weight, the adhesion to a polyolefin substratetends to be inadequate. It is preferably at least 15 parts by weight,more preferably at least 20 parts by weight. If the amount of thepolyolefin (A) exceeds 90 parts by weight, the physical properties of acoating film obtainable from such a composite aqueous resin dispersion,specifically, the strength, water resistance, weather resistance,abrasion resistance, solvent resistance, etc. of the coating film, tendto be inadequate. It is preferably at most 85 parts by weight, morepreferably at most 80 parts by weight.

The weight ratio of the total amount of the polymer (C) and said anotherresin to water is preferably from 5:95 to 60:40. Namely, based on 100parts by weigh of the total amount of the polymer (C), another resin andwater, the total amount of the polymer (C) and another resin is at least5 parts by weight and at most 60 parts by weight. If the total amount isless than 5 parts by weight, the working efficiency for coating,heat-curing, etc. tends to be poor, such being not practical. It ispreferably at least 10 parts by weight, more preferably at least 15parts by weight. If it exceeds 60 parts by weight, the viscosity of theaqueous resin dispersion tends to be too high, the coating propertytends to deteriorate, and a uniform coating film tends to be hardlyformed. It is preferably at most 55 parts by weight, more preferably atmost 50 parts by weight.

In order to emulsify said another resin to form an aqueous resindispersion, a surfactant may be used as the case requires. As such asurfactant, one mentioned in (5) may, for example, be used.

The content of the surfactant is usually at most 20 parts by weight per100 parts by weight of the resin. It is preferably at most 10 parts byweight, more preferably at most 5 parts by weight, further preferably atmost 2 parts by weight as the content of the surfactant is small,bleeding out of the surfactant tends to hardly take place. Mostpreferably, the surfactant is not substantially used.

Further, the surfactant may be used also in the method wherein thepolymer (C) and the resin are mixed and then emulsified.

Said another resin is preferably at least one resin selected from thegroup consisting of an acrylic resin, a polyester resin, a polyurethaneresin, an epoxy resin and a vinyl ester resin. The resin dispersioncontaining such a resin is suitable for a coating material. Hereinafter,such a resin will be generally referred to as a resin (D). With respectto a description of the resin (D), the description of resin (ID) in(5-1) under “WITH RESPECT TO THE SECOND EMBODIMENT” applies.

(5-2) Addition of Pigment

A pigment (E) may be added to the resin dispersion of the presentinvention. The aqueous resin dispersion containing the pigment (E) issuitable as a coating material.

The pigment which may be used is not particularly limited and may, forexample, be a coloring pigment, such as an inorganic pigment such astitanium oxide, carbon black, iron oxide, chromium oxide, iron blue, redoxide, chrome yellow or yellow oxide, or an organic pigment such as anazo pigment, an anthracene pigment, a perynone pigment, a perylenepigment, a quinacridone pigment, an isoindolynone pigment, an indigopigment or a phthalocyanine pigment; an extender pigment such as talc,calcium carbonate, clay, kaolin, silica or precipitated barium sulfate;a conductive pigment such as conductive carbon or whiskers coated withantimony-doped tin oxide; or a colorless or colored metal glitter suchas a metal or alloy such as aluminum, copper, zinc, nickel, tin oraluminum oxide. They may be used alone or in combination as a mixture oftwo or more of them.

The amount of the pigment (E) to be added to the resin dispersion ispreferably at least 10 parts by weight per 100 parts by weight of theresins (the total amount of the polymer (C) and other resins). It ismore preferably at least 50 parts by weight. However, it is preferablyat most 400 parts by weight, more preferably at most 200 parts byweight. As the amount increases from the lower limit value, thecolor-forming or hiding property tends to be high, and as the amount issmaller than the upper limit value, the adhesion, moisture resistanceand oil resistance tend to be high.

At that time, a pigment dispersant may be employed. For example, anaqueous acrylic resin such as JONCRYL resin manufactured by JohnsonPolymer Corporation; an acidic block copolymer such as BYK-190manufactured by BYK-Chemie; a styrene-maleic acid copolymer; anacetylene diol derivative such as SURFYNOL T324 manufactured by AirProducts; a water-soluble carboxymethylacetate butyrate such asCMCAB-641-0.5 manufactured by Eastman Chemical Company, may, forexample, be mentioned. By using such a pigment dispersant, a stablepigment paste can be prepared.

As a method for dispersing the pigment (E) in the resin dispersion ofthe present invention, a known method may be employed without anyparticular restriction. For example, the pigment may be preliminarilymixed with water, a pigment dispersant, a thickener, a defoaming agent,etc., to prepare a pigment base, and then, this pigment base may bemixed with the aqueous resin dispersion. If necessary, a freeze-thawstabilizer, a film-forming assistant, an antiseptic or a mildewcide may,for example, be incorporated. Otherwise, the pigment, water, the aqueousresin dispersion and other additives may simultaneously be mixed. Formixing, a mixer such as a dissolver, a homogenizer or a homomixer, or adispersing machine such as a paint shaker, a ball mill, a sand mill, anattractor, a roll mill or a kneader, may be employed.

The resin dispersion of the present invention is useful for a primer, aprimerless coating material, an adhesive, an ink, etc. The presentinvention is particularly useful for a primer, a coating material or anadhesive. It is particularly suitable for a polyolefin substrate. Forexample, it is useful as a coating material for automobiles such as forinterior or exterior of automobiles, a coating material for homeelectronics such as mobile phones or personal computers or a coatingmaterial for building materials.

(6) Laminate

The resin dispersion of the present invention or a coating materialcontaining it may be applied and heated on a substrate to form a resinlayer thereby to obtain a laminate. This resin layer is a layercomprising a polymer (C) having a hydrophilic polymer (B) bonded to apolyolefin (A) in a ratio of (A):(B)=100:5 to 100:500 (weight ratio).

Such a laminate is useful for various applications for e.g. automobiles,home electronics or buildings. The substrate may be of any form such asa film, sheet or plate.

The resin dispersion of the present invention may be applied on a moldedproduct (a substrate) of an olefin polymer having crystallinity to forma coating film. The olefin polymer as the substrate may, for example, bean olefin polymer such as high pressure method polyethylene, medium orlow pressure method polyethylene, polypropylene,poly-4-methyl-1-pentene, poly-1-butene or polystyrene, or an olefincopolymer such as an ethylene-propylene copolymer, an ethylene-butenecopolymer or a propylene-butene copolymer. Among these olefincopolymers, a propylene polymer is preferably employed. Further, it maybe used also for the surface treatment of a molded product made ofpolypropylene and synthetic rubber, a molded product made of a polyamideresin, an unsaturated polyester resin, a polybutylene terephthalateresin or a polycarbonate resin, such as a molded product such as abumper for an automobile, a steel plate, or a steel plate forelectrodeposition.

The molded product to which the resin dispersion of the presentinvention may be applied, may be one obtained by molding any one of theabove-mentioned various polymers or resins by any method selected fromknown molding methods such as injection molding, compression molding,blow molding, extrusion molding and rotation molding.

Also in a case where an inorganic filler such as talc, zinc white, glassfiber, titanium white or magnesium sulfate, a pigment, etc., isincorporated to such a molded product, it is possible to form a coatingfilm with good adhesion.

(6-1) Method for Producing Laminate

The method for forming a resin layer on a substrate is not particularlylimited, and a conventional method may be used. For example, variouscoating methods for the resin dispersion or the coating material may bementioned such as spray coating, bar coating, spin coating, dip coating,gravure coating, etc. Usually, coating by spray coating is carried outon large size molded products such as bumpers for automobiles or homeelectronic products, and coating by gravure coating or bar coating iscarried out on plastic films or sheets.

After applying the resin dispersion or the coating material, the coatedfilm is cured usually by heating by a nichrome wire, infrared ray orradiofrequency wave to obtain a laminate having a desired coated film onits surface. The conditions for curing the coated film are suitablyselected depending upon the material and shape of the substrate, thecomposition of the coating material used, etc. The curing temperature isnot particularly limited, but in consideration of practical efficiency,it is usually at least 50° C., preferably at least 60° C. However, it isusually at most 150° C., preferably at most 130° C.

The thickness (after curing) of the resin layer to be laminated maysuitably selected depending upon the material and shape of thesubstrate, the composition of the coating material used, etc., but it isusually at least 0.1 μm, preferably at least 1 μm, more preferably atleast 5 μm. However, it is usually at most 500 μm, preferably at most300 μm, more preferably at most 200 μm, particularly preferably at most100 μm.

(6-2) Thermoplastic Resin Molded Product (F)

As the substrate for the laminate of the present invention, athermoplastic resin molded product is preferred. The thermoplastic resinmolded product (F) is not particularly limited, and for example, it is amolded product made of a polyolefin resin, a polyamide resin, apolyethylene terephthalate resin, a polybutyrene terephthalate resin ora polycarbonate resin. Among them, the present invention is preferablyapplicable to a thermoplastic resin molded product (F) made of apolyolefin resin (hereinafter referred to as a polyolefin moldedproduct). And it is particularly preferably applicable to athermoplastic resin molded product (F) made of a propylene polymer(hereinafter referred to as a propylene polymer molded product).

The polyolefin molded product is usually a molded product of crystallinepolyolefin, and known various polyolefins may be employed without anyparticularly restriction. For example, a homopolymer of ethylene orpropylene, a copolymer of ethylene and propylene, a copolymer ofethylene or/and propylene with another comonomer such as an α-olefincomonomer having at least two carbon atoms, such as 1-butene, 1-pentene,1-hexene, 1-heptene, 1-octene, cyclopentene, cyclohexane or norbornene,or a copolymer of two or more types of such comonomers, may be used.

As the α-olefin comonomer, a C₂₋₆ α-olefin comonomer is preferred.Further, a copolymer of an α-olefin monomer with a comonomer such asvinyl acetate, an acrylic acid ester or a methacrylic acid ester, acopolymer thereof with a comonomer such as an aromatic vinyl monomer, orits hydrogenated product, or a hydrogenated product of a conjugateddiene block copolymer may, for example, be also used. Here, when asimple term of a copolymer is used, it may be a random copolymer or ablock copolymer. Further, the polyolefin may be modified as the caserequires.

They may be used alone or in combination as a mixture depending upon theparticular application.

The melt flow rate (MFR: 230° C., load: 2.16 kg) of the polyolefin ispreferably at least 2 g/10 min, more preferably at least 10 g/10 min,particularly preferably at least 25 g/10 min. However, it is preferablyat most 300 g/10 min, more preferably at most 200 g/10 min. When MFR ishigher than the lower limit value, the flowability of the polyolefintends to increase. Inversely, when MFR is lower than the upper limitvalue, the mechanical properties tend to be high. MFR of the polyolefinmay be adjusted during the polymerization or may be adjusted after thepolymerization by an organic peroxide such as diacyl peroxide or dialkylperoxide.

The polyolefin is more preferably a propylene polymer molded product.The propylene polymer molded product is usually a molded product of acrystalline propylene polymer, and a known product may be employed. Forexample, a homopolymer of propylene, or a copolymer of propylene withother comonomer, for example, at least one member of α-olefin typecomonomers having at least two carbon atoms, such as ethylene, 1-butene,1-pentene, 1-hexene, 1-heptene, 1-octene, cyclopentene, cyclohexane andnorbornene, may be employed.

Preferred is a propylene homopolymer and/or propylene-ethylenecopolymer. Here, a propylene-ethylene copolymer is a propylene-ethylenerandom copolymer and/or a propylene-ethylene block copolymer, morepreferably a propylene-ethylene block copolymer. Here, apropylene-ethylene block copolymer comprises crystalline polypropyleneportions (a unit portions) and ethylene-propylene random copolymerportions (b unit portions).

The above a unit portions are obtained usually by homopolymerization ofpropylene, or in some cases, by copolymerization of propylene with asmall amount of another α-olefin.

MFR (MFR: 230° C., load: 2.16 kg) of the polypropylene homopolymer forthe a unit portions is preferably at least 10 g/10 min, more preferablyat least 15 g/10 min, further preferably at least 20 g/10 min,particularly preferably at least 40 g/10 min. Further, it is preferablyat most 500 g/10 min, more preferably at most 400 g/10 min, furtherpreferably at most 300 g/10 min.

As this MFR is higher than the lower limit value, the fluidity tends toincrease. Inversely, as MFR is lower than the above upper limit value,the mechanical properties tend to be high.

On the other hand, the b unit portions are a rubber component obtainableby random copolymerization of propylene and ethylene. The propylenecontent in the propylene-ethylene random copolymer portion of the b unitportions is preferably at least 30 wt %, more preferably at least 40 wt%, further preferably at least 50 wt %. However, it is preferably atmost 85 wt %, more preferably at most 80 wt %, further preferably atmost 75 wt %. When the propylene content is within this range, itsdispersibility and the glass transition temperature will be in properranges, and the impact properties tend to be good. The propylene contentcan be adjusted by controlling the concentration ratio of propylene toethylene at the time of polymerization of the propylene-ethylene randomcopolymer portion.

The molecular weight of the propylene-ethylene random copolymer portionof the b unit portions is not particularly limited. However, inconsideration of the dispersibility and impact resistance, the weightaverage molecular weight (Mw) is preferably from 200,000 to 3,000,000,more preferably from 300,000 to 2,500,000, further preferably from400,000 to 2,000,000.

The amounts of the a unit portions and the b unit portions are notparticularly limited. However, usually, the a unit portions arepreferably at most 95 wt %, more preferably from 50 to 95 wt %, furtherpreferably from 60 to 90 wt %, based on the entire amount, and the bunit portions are preferably at least 5 wt %, more preferably from 5 to50 wt %, further preferably from 10 to 40 wt %, based on the entireamount. When the amount of the b unit portions is higher than the lowerlimit value, the impact resistance tends to be high, and when it islower than the upper limit value, the rigidity, strength and heatresistance tend to be high.

In the present invention, the amount of the b unit portions is measuredby means of a temperature-raising elution fractionation method. Namely,in extraction with o-dichlorobenzene, the a unit portions will not beeluted at a temperature of at most 100° C., but the b unit portions willbe easily eluted. Accordingly, the propylene-ethylene block copolymerafter the production is subjected to the above extraction analysis bymeans of o-dichlorobenzene, whereby the composition is determined.

The ratio of the amounts of the a unit portions and the b unit portionsis determined by the polymerization amount of the propylene homopolymerportion and the polymerization amount of the propylene-ethylene randomcopolymer portion. Accordingly, it can be adjusted, for example, bycontrolling the respective polymerization periods of time.

The method for producing the propylene homopolymer and thepropylene-ethylene block copolymer are not particularly limited, andthey are suitably selected from known methods and conditions.

As a polymerization catalyst for propylene, a highly stereoregularcatalyst is usually employed. For example, a catalyst obtained bycombining an organic aluminum compound and an aromatic carboxylic acidester, with a titanium trichloride composition obtained by reducingtitanium tetrachloride with an organic aluminum compound and furthertreating it with various electron donors and electron acceptors(JP-A-56-100806 (U.S. Pat. No. 4,533,705), JP-A-56-120712 (U.S. Pat. No.4,309,521), or a supported catalyst obtained by contacting a magnesiumhalide with titanium tetrachloride and various electron donors(JP-A-57-63310 (U.S. Pat. No. 5,539,067)) may, for example, bementioned. Further, a metallocene catalyst as shown in WO91/04257 (U.S.Pat. No. 5,026,796) may also be mentioned. Here, the metallocenecatalyst may not contain alumoxane, but preferred is a catalyst having ametallocene compound and alumoxane combined i.e. a so-called Kaminskycatalyst.

The propylene-ethylene block copolymer is obtained by firstlyhomo-polymerizing propylene in the presence of the above catalyst byapplying a production process such as a gas phase polymerization method,a liquid phase bulk polymerization method or a slurry polymerizationmethod, followed by random polymerization of propylene and ethylene. Inorder to obtain a propylene-ethylene block copolymer having theabove-mentioned melting properties (MFR), it is preferred to carry outmulti-stage polymerization by using a slurry method or a gas phasefluidized bed method. Otherwise, it can be obtained by a method ofcarrying out homopolymerization of propylene by multistages, followed byrandom polymerization of propylene and ethylene. In a case where apropylene-ethylene block copolymer having a large amount of the b unitportions is to be prepared, a gas phase fluidized bed method isparticularly preferred.

The propylene homopolymer is obtained by polymerizing propylene alone inthe presence of the above catalyst by applying a production process suchas a gas phase polymerization method, a liquid phase bulk polymerizationmethod or a slurry polymerization method. In order to obtain a propylenehomopolymer having the above-mentioned melting properties, it ispreferred to carry out multistage polymerization by using a slurrymethod or a gas phase fluidized bed method.

The propylene homopolymer and the propylene-ethylene block copolymer ofthe present invention are desired to be excellent in mechanicalproperties and have high rigidity and impact resistance, so that theyare useful as structural materials. Namely, the flexural modulus ispreferably at least 300 MPa, more preferably from 500 to 3,000 MPa,further preferably from 1,000 to 2,000 MPa. Within such range, they willbe excellent in rigidity and will be ones suitable as structuralmaterials. Further, the IZOD impact strength is preferably at least 1kJ/m², more preferably from 2 to 100 kJ/m², further preferably from 5 to80 kJ/m², particularly preferably from 8 to 60 kJ/m². Within this range,they will be excellent in impact resistance and will be ones suitable asstructural materials.

The thermoplastic resin molded products may be used alone or in acombination of two or more of them.

(6-3) Inorganic Filler Component

The thermoplastic resin molded product (F) to be used in the presentinvention may contain an inorganic filler component.

Particularly, by incorporating an inorganic filler component to acrystalline polyolefin, it is possible to improve the mechanicalproperties such as the flexural modulus, rigidity, etc., of the moldedproduct.

Specifically, a plate-form filler such as talc, mica or montmorillonite;a fiber-form filler such as short glass fiber, long glass fiber, carbonfiber, alamide fiber, alumina fiber, boron fiber or zonolite; aneedle-form (whisker) filler such as potassium titanate, magnesiumoxysulfate, silicon nitride, aluminum borate, basic magnesium sulfate,zinc oxide, wollastonite, calcium carbonate or silicon carbonate; aparticle-form filler such as precipitated calcium carbonate, heavycalcium carbonate or magnesium carbonate; or a balloon-form filler suchas glass balloon, may, for example, be mentioned. An inorganic filler orpigment such as zinc white, titanium white or magnesium sulfate may alsobe used. Among them, from the balance of the physical properties andcosts, talc, mica, glass fiber or whisker is preferred, and morepreferred is talc, mica or glass fiber.

The inorganic filler component may be surface-treated with e.g. asurfactant or coupling agent. The surface-treated filler has an effectto further improve the strength or heat resistant rigidity of the moldedproduct.

The amount of the inorganic filler component to be used, is selectedwithin a wide range depending upon the purpose and application of themolded product. It is preferably from 1 to 80 parts by weight, morepreferably from 2 to 75 parts by weight, further preferably from 5 to 60parts by weight, per 100 parts by weight of the crystalline polyolefin.

By incorporating the inorganic filler component, the flexural modulus ofthe crystalline polyolefin can be improved to be preferably at least1,000 MPa, more preferably 1,500 to 10,000 MPa, further preferably from2,000 to 8,000 MPa. Further, the IZOD impact strength can be improved tobe preferably at least 1 kJ/m², more preferably from 2 to 80 kJ/m²,further preferably from 4 to 60 kJ/m².

Such inorganic fillers may be used alone or in combination as a mixtureof two or more of them.

Now preferred fillers will be described in detail.

(1) Talc

The average particle diameter of talc to be used in the presentinvention is usually at most 10 μm, preferably from 0.5 to 8 μm, morepreferably from 1 to 7 μm. The average particle diameter value is aparticle diameter value at 50 wt. % of the cumulative amount read outfrom a particle size cumulative distribution curve drawn from theresults of measurement by a laser diffraction method (such as LA920W,manufactured by HORIBA, Ltd.) or by a liquid phase precipitation systemlight transmission method (such as CP model, manufactured by ShimadzuCorporation). The value in the present invention is an average particlediameter value measured by the laser diffraction method.

As such talc, fine particulate one obtainable by mechanically finelypulverizing natural talc and further precisely classifying it, is used.One once roughly classified may further be classified.

As the mechanical pulverization method, a method of employing apulverizer such as a jaw crusher, a hummer crusher, a roll crusher, ascreen mill, a jet pulverizer, a colloid mill, a roller mill or avibration mill may be mentioned. The pulverized talc was once orrepeatedly classified in a wet system or dry system by an apparatus suchas a cyclone, a cyclone air separator, a microseparator or a sharp cutseparator, to adjust the size to the above-mentioned average particlediameter.

As a method for producing talc for the present invention, it ispreferred to carry out the classification operation by a sharp cutseparator after pulverizing it to a specific particle size.

Such talc may be surface-treated with various organic titanate couplingagents, organic silane coupling agents, modified polyolefins having anunsaturated carboxylic acid or its anhydride grafted, fatty acids, metalsalts of fatty acids, or fatty acid esters, for the purpose of improvingthe adhesion to the polymer or the dispersibility.

(2) Glass Fiber

As glass fiber, it is common to employ glass chopped strands. The lengthof such glass chopped strands is usually from 3 to 50 mm, and thediameter of the fibers is usually from 3 to 25 μm, preferably from 8 to14 μm.

As such glass chopped strands, it is preferred to employ ones havingsurface modification applied by means of a silane compound or havingsurface treatment applied by means of e.g. a polyvinyl alcohol, apolyvinyl acetate, a polyurethane, an epoxy resin or a bundling agentsuch as an olefin component.

The olefin component as a bundling agent may, for example, be anunsaturated carboxylic acid-modified polyolefin or a low molecularweight polyolefin.

In the present invention, in order to improve the mechanical strength bythe interfacial adhesion of the crystalline polyolefin and the glassfiber, a polyolefin modified by an unsaturated carboxylic acid and/orits derivative may be incorporated. Particularly preferred is onemodified, with a polypropylene being the matrix, and it is preferred toemploy one having a modification ratio of from 0.1 to 10 wt %.

(3) Mica

Mica is preferably one having an average particle diameter of from 2 to100 μm and an average aspect ratio of at least 10, more preferably onehaving an average particle diameter of from 2 to 80 μm and an averageaspect ratio of at least 15. When the average particle diameter of micais within the above range, it is possible to more improve the scratchresistance and impact strength of the molded product and to preventdeterioration of the exterior appearance.

Further, the mica may be any one of so-called white mica, gold mica andblack mica. However, gold mica or white mica is preferred, and whitemica is more preferred.

The method for producing mica is not particularly limited, and it may beproduced by a method similar to the above-mentioned method for producingtalc. A dry pulverization-wet classification system or a wetpulverization-wet classification system is preferred. The wetpulverization-wet classification system is more preferred.

(6-4) Elastomer Component

In a case where the thermoplastic resin molded product (F) to be used inthe present invention is a crystalline polyolefin molded product, anelastomer component may further be incorporated, whereby it is possibleto improve the impact resistant strength of the molded product.

Such an elastomer component may, for example, be an ethylene-α-olefinrandom copolymer rubber, an ethylene-α-olefin-non-conjugated dienecopolymer rubber or a styrene-containing thermoplastic elastomer. As aspecific example, an ethylene-α-olefin copolymer rubber such as anethylene-propylene copolymer rubber, an ethylene-1-butene copolymerrubber, an ethylene-1-hexene copolymer rubber or an ethylene-1-octenecopolymer rubber; an ethylene-α-olefin-non-conjugated diene copolymerrubber such as an ethylene-propylene-ethylidene norbornene copolymerrubber (EPDM) or a styrene-containing thermoplastic elastomer such as ahydrogenated product of styrene-butadiene-styrene triblock (SEBS) or ahydrogenated product of styrene-isoprene-styrene triblock (SEPS), may bementioned.

These elastomers may be produced as described below.

MFR (230° C., load: 2.16 kg) of such an elastomer component ispreferably from 0.5 to 150 g/10 min, more preferably from 0.7 to 100g/10 min, further preferably from 0.7 to 80 g/10 min, when exteriormaterial for automobiles is taken into consideration as one of the mainapplications of the present invention.

Such elastomer components may be used alone or in combination as amixture of two or more of them.

(6-5) Other Components

The thermoplastic resin molded product (F) may contain, in addition tothe above components, optional additives or blend components within arange not to substantially impair the effects of the present invention.Specifically, a coloring pigment, an antioxidant of e.g. phenol type,sulfur type or phosphorus type, an antistatic agent, a photostabilizersuch as a hindered amine, an ultraviolet absorber, various nucleatingagents such as organic aluminum talc, a dispersant, a neutralizingagent, a blowing agent, a copper inhibitor, a lubricant, a flameretardant, and a resin such as a polyethylene resin, may, for example,be mentioned.

(6-6) Method For Producing Thermoplastic Resin Molded Product (F)

To the above-mentioned resin, various components are blended as the caserequires, followed by mixing and melt-kneading. The kneading method isnot particularly limited, and by kneading and granulating by means of ausual kneading machine such as a single screw extruder, a twin screwextruder, a banbury mixer, a roll mixer, a bravender plastograph or akneader, a thermoplastic resin composition to constitute thethermoplastic resin molded product (F) of the present invention will beobtained. It is preferred to employ a twin screw extruder in order tolet the respective components be well dispersed.

At the time of such kneading and granulation, the above-mentionedrespective components may simultaneously be kneaded, or in order toimprove the performance, the respective components may be separatelykneaded.

Then, the thermoplastic resin composition is molded to obtain thethermoplastic resin molded product (F). As a molding method, variousknown methods may be employed.

For example, injection molding (inclusive of gas injection molding),compression molding, injection compression molding (press injection),extrusion molding, blow molding, rotational molding, calendar molding,inflation molding, uniaxially stretched film forming or biaxialstretched film forming may, for example, be mentioned. Preferably,injection molding, compression molding or injection compression moldingis employed, and in consideration of the productivity, etc., injectionmolding is particularly preferred.

(6-7) Application of Laminate

The laminate of the present invention is excellent in coating filmadhesion and further has an excellent physical property balance withrespect to rigidity and impact resistance. Further, in a case where theresin layer constituting the laminate contains substantially nosurfactant, there will be no bleeding out, and the exterior appearancewill be excellent. Further, it is not required to contain a halogen suchas chlorine, whereby the environmental load can be reduced.

Accordingly, the laminate of the present invention is useful for variousindustrial components for e.g. automobiles, home electronic products andbuilding materials, and it provides a practically sufficient performanceas a component or material which is made to have a thin wall thickness,a high functionality or a large size.

For example, it can be used as a molding material for various industrialcomponents, such as an automobile component such as a bumper, aninstrument panel, a trim or a garnish; a home electronic instrumentcomponent such as a TV casing, a washing machine vessel, a refrigeratorcomponent, an air conditioner component or a cleaner component; atoiletry component such as a toilet sheet, a toilet sheet cover or awater tank; a component around a bathroom such as a bath tub, a wall ofa bathroom, a ceiling or drainage.

With Respect to the Second Embodiment

An aqueous resin dispersion of the present invention has particles madeof a polymer (IC) containing a propylene polymer (IA) and particles madeof at least one resin (ID) selected from the group consisting of anacrylic resin, a polyester resin, a polyurethane resin, an epoxy resinand a vinyl ester resin, respectively dispersed in water, and satisfiesthe following (1) to (4):

(1) the weight ratio of the propylene polymer (IA) to the resin (ID) isfrom 90:10 to 10:90,

(2) the weight ratio of the total amount of the polymer (IC) and theresin (ID) to water is from 5:95 to 60:40,

(3) the content of a surfactant is at most 10 parts by weight per 100parts by weight of the total amount of the polymer (IC) and the resin(ID), and

(4) the 50% particle diameter of the particles made of the polymer (IC)is at most 0.5 μm and at most 0.9 time of the 50% particle diameter ofthe particles of the resin (ID).

By the use of the resin (ID) in combination with the polymer (IC), it ispossible to obtain not only high adhesion to a polyolefin substrate bythe polymer (IC) but also high adhesion to a resin other than polyolefinwhich can not be accomplished by the polymer (IC) alone. Further, thereis a merit such that the physical properties such as the strength, waterresistance, weather resistance, abrasion resistance and solventresistance of the coating film, can be improved. Further, it iseffective also to improve the external appearance of the coating(glazing or delustering) or to reduce tackiness.

In the present invention, in order to let the polymer (IC) and the resin(ID) exhibit the respective characteristics effectively, particles madeof the polymer (IC) and particles made of the resin (ID) arerespectively separately dispersed in water. Such an aqueous resindispersion may, for example, be obtained by mixing a dispersion havingthe polymer (IC) emulsified and dispersed in water, with a dispersionhaving the resin (ID) emulsified and dispersed in water.

The weight ratio of the propylene polymer (IA) to the resin (ID) is from90:10 to 10:90. Namely, based on 100 parts by weight of the total amountof the propylene polymer component and other resins, the amount of thepropylene polymer (IA) is at least 10 parts by weight and at most 90parts by weight. If the amount of the propylene polymer (IA) is lessthan 10 parts by weight, the adhesion to a propylene polymer substratetends to be inadequate. It is preferably at least 15 parts by weight,more preferably at least 20 parts by weight. If the amount of thepropylene polymer (IA) exceeds 90 parts by weight, the physicalproperties of a coating film obtainable from such a composite aqueousresin dispersion, specifically the strength, water resistance, weatherresistance, abrasion resistance, solvent resistance, etc. of the coatedfilm, tend to be inadequate. It is preferably at most 80 parts byweight, more preferably at most 70 parts by weight.

The weight ratio of the total amount of the polymer (IC) and the resin(ID) to water is from 5:95 to 60:40. Namely, based on 100 parts byweight of the total amount of the polymer (IC), the resin (ID) andwater, the total amount of the polymer (IC) and the resin (ID) is atleast 5 parts by weight and at most 60 parts by weight. If it is lessthan 5 parts by weight, the working efficiency in e.g. the coating orheat-curing tends to be poor, such being not practical. It is preferablyat least 10 parts by weight, more preferably at least 15 parts byweight. If it exceeds 60 parts by weight, the viscosity of the aqueousresin dispersion tends to be too high, and the coating property tends tobe poor, and it tends to be difficult to form a uniform coating film. Itis preferably at most 55 parts by weight, more preferably at most 50parts by weight.

The content of a surfactant is at most 10 parts by weight per 100 partsby weight of the resin component (the total amount of the polymer (IC)and the resin (ID)). Further, the 50% particle diameter of the particlesmade of the polymer (IC) is at most 0.5 μm and at most 0.9 time of the50% particle diameter of the particles of the resin (ID).

The propylene copolymer (IA) in the present invention is excellent indispersibility in water, and even without using or using a very smallamount of a surfactant, it is possible to obtain an aqueous resindispersion wherein the dispersed particle sizes are fine, the particlesize distribution is narrow, and the particles are dispersed stably.Thus, when the resin dispersion of the present invention is used as acoating material, bleeding out can be prevented, and it is possible toobtain a coated product excellent in the exterior appearance, and it isalso possible to improve the water resistance or oil resistance (GHresistance) of the coating.

The 50% particle diameter of the polymer (IC) particles is preferably atmost 0.3 μm, more preferably at most 0.2 μm, most preferably at most 0.1μm. When the 90% particle diameter is likewise obtained, morepreferably, the 90% particle diameter can be made to be at most 1 μm,particularly preferably at most 0.5 μm. By reducing the dispersedparticle sizes, it is possible to improve the dispersion stability toprevent agglomeration and to disperse the particles more stably.Further, the ratio of the 90% particle diameter to the 50% particlediameter being small, means that the particle size distribution isnarrow, and consequently, the dispersion stability will be improved.

By reducing the particle diameter of the polymer (IC) particles to alevel of at most 0.9 time of the particle diameter of the resin (ID)particles, when a coating film is formed, spaces among the resin (ID)particles will be filled with the polymer (IC) particles, and the volumeof spaces will be small, whereby the adhesion to a substrate will behigh, and the water resistance and solvent resistance will be improved.Further, in the coated film, a sea-islands structure is formed whereinthe propylene polymer having a high adhesion to a propylene polymersubstrate constitutes “sea”, and other binder resins providing otherfunctions to the coated film constitutes “islands”, whereby there willbe a merit such that the adhesion to a substrate will be higher, and thewater resistance and the solvent resistance will be improved. Theparticle diameter of is the polymer (IC) particles is preferably at most0.8 time, more preferably at most 0.6 time, of the particle diameter ofthe resin (ID) particles.

The polymer (IC) is preferably one having a hydrophilic polymer (IB) oran acidic group bonded to a propylene polymer (IA). Such a polymer (IC)is excellent in dispersibility in water, whereby without using or usinga very small amount of a surfactant, it is possible to obtain an aqueousresin dispersion wherein dispersed particle sizes are fine, the particlesize distribution is narrow, and the particles are dispersed stably.

More preferably, the polymer (IC) is one having the hydrophilic polymer(IB) bonded to the propylene polymer (IA) in a ratio of (IA):(IB)=100:5to 100:500 (weight ratio). The ratio of the propylene polymer (IA) tothe hydrophilic polymer (IB) is (IA):(IB)=100:5 to 100:500 parts byweight. If the ratio of the hydrophilic polymer (IB) is smaller thanthis range, the polymer (IC) will not be well dispersed in water, thedispersed particle sizes tend to be very large, whereby the particlestend to be agglomerated or separated. On the other hand, if the ratio ofthe hydrophilic polymer (IB) is larger than this range, the adhesion toa propylene polymer substrate tends to be poor.

The method for producing the polymer (IC) by bonding the hydrophilicpolymer (IB) to the propylene polymer (IA), may usually be a method(IR1) wherein a hydrophilic monomer is polymerized in the presence ofthe propylene polymer (IA) to form the hydrophilic polymer (IB) bondedto the propylene polymer (IA), or a method (IR2) wherein a preliminarilypolymerized hydrophilic polymer (IB) is bonded to the propylene polymer(IA). Either method may suitably be selected for use depending upon thetypes and combination of the polyolefin and the hydrophilic polymer, thedesired properties of the polymer (IC), etc. Further, as the polyolefin(A) a polypropylene polymer (IA1) having no reactive group or apolypropylene polymer (IA2) having reactive groups may be used.

Now, more detailed descriptions will be given.

(1) Propylene Polymer (IA)

The propylene polymer (IA) of the present invention is a polymer havinga propylene content of at least 50 mol %. The propylene content ispreferably at least 60 mol %, more preferably at least 70 mol %.Usually, as the propylene content is high, the adhesion to apolypropylene substrate tends to increase.

As the propylene polymer (IA) of the present invention, a propylenepolymer (IA1) having no reactive group or a propylene polymer (IA2)having reactive groups may be used.

(1-1) Propylene Polymer (IA1) Having No Reactive Group

As the propylene polymer (IA1), known various propylene polymers andmodified propylene polymers may be used without any particularrestrictions. For example, a homopolymer of propylene, a copolymer ofethylene and propylene, a copolymer of propylene with another comonomer,for example, an α-olefin comonomer having at least two carbon atoms,such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,cyclopentene, cyclohexene or norbornene, or a copolymer of two or moreof such comonomers, may be used. The α-olefin comonomer is preferably aC₂₋₆ α-olefin comonomer, more preferably a C₂₋₆ α-olefin comonomer.

Further, a copolymer of propylene with a comonomer such as vinylacetate, an acrylic acid ester or a methacrylic acid ester, ahydrogenated product of a copolymer of two or more monomers selectedfrom aromatic vinyl monomers and conjugated diene monomers, may, forexample, be used. Here, when a copolymer is simply mentioned, it may bea random copolymer or a block copolymer. Further, a chlorinatedpropylene polymer having such a propylene polymer chlorinated, may alsobe used. The chlorination degree of such a chlorinated propylene polymeris usually at least 5 wt %, preferably at least 10 wt %, and thechlorination degree is usually at most 50 wt %, preferably at most 30 wt%.

Specifically, the propylene polymer (IA1) may, for example, be apolypropylene, an ethylene-propylene copolymer, a propylene-butenecopolymer, an ethylene-propylene-butene copolymer, a propylene-hexenecopolymer, a chlorinated polyethylene, a chlorinated ethylene-propylenecopolymer or a chlorinated propylene-butene copolymer. Preferred is apropylene homopolymer, or a copolymer of propylene with other α-olefin.They may be chlorinated. More preferred is a propylene homopolymer, anethylene-propylene copolymer, a propylene-butene copolymer, anethylene-propylene-butene copolymer, a chlorinated polypropylene, achlorinated ethylene-propylene copolymer, or a chlorinatedpropylene-butene copolymer.

They may be used alone or in combination as a mixture of two or more ofthem.

The propylene polymer (IA1) in the present invention preferably has aweight average molecular weight Mw of from 1,000 to 500,000, as measuredby GPC and calculated by a calibration curve of each propylene polymer.The lower limit value is more preferably 10,000, further preferably30,000, particularly preferably 50,000. The upper limit value is morepreferably 300,000, further preferably 250,000, particularly preferably200,000. As Mw becomes higher than the lower limit value, stickinesstends to be less, and the adhesion to the substrate tends to increase,and as it becomes lower than the upper limit value, the viscosity tendsto be low, whereby the preparation of the resin dispersion tends to beeasy. Here, the GPC measurement is carried out by a conventional methodemploying a commercially available apparatus and by using e.g.o-dichlorobenzene as a solvent.

One of the most preferred forms of the propylene homopolymer orcopolymer is one having entirely or partially an isotactic structure asstereoregularity. For example, not only a usual isotactic polypropylenebut also an isotactic block polypropylene or a stereo-blockpolypropylene may be used.

Preferably, the propylene polymer (IA1) is a homopolymer or copolymer ofa stereo-block polypropylene having isotactic blocks and atactic blocks.Most preferred is a stereo-block polypropylene polymer having isotacticblocks and atactic blocks.

More preferably, when peaks derived from the carbon atom of a methylgroup of a propylene unit chain portion of a head-to-tail linkage, areobserved by ¹³C-NMR and the chemical shift of a peak top of a peakattributable to a pentad represented by mmmm is set to be 21.8 ppm, theratio (S₁/S) of the area S₁ of a peak having a peak top at 21.8 ppm tothe total area S of peaks appearing from 19.8 ppm to 22.1 ppm, is from20% to 70%. The lower limit value is preferably 30%, further preferably35%, particularly preferably 40%. The upper limit value is preferably65%, more preferably 60%, particularly preferably 55%. As it is higherthan the lower limit value, the stickiness tends to be less, and as itis lower than the upper limit value, the crystallinity tends to be low,and preparation of the resin dispersion tends to be easy.

Further preferably, when the area of a peak (mmmr) having a peak topfrom 21.5 to 21.7 ppm is represented by S₂, 4+2S₁/S₂>5.

Further, it is preferred that the propylene polymer (IA1) is apropylene-α-olefin copolymer, which has a propylene content of from 50mol % to 95 mol %, and the molecular weight distribution Mw/Mn of thepolymer (IA1) is at most 3.0. Such a copolymer has a melting point lowerthan the propylene homopolymer and thus has a merit that with a resindispersion employing it, the baking temperature after the coating can belowered. The α-olefin is preferably a C₂₋₈ α-olefin, more preferably aC₂₋₆ α-olefin, further preferably a C₂₋₄ α-olefin, most preferably1-butene.

Usually, as the propylene content is high, the adhesion to apolypropylene substrate tends to increase. It is preferably at least 60mol %, more preferably at least 70 mol %. However, the propylene contentis at most 95 mol %. Usually, by lowering the propylene content, themelting point of the copolymer can be lowered, and for example, therewill be a merit such that the baking temperature after coating can belowered. It is preferably at most 90 mol %, more preferably at most 85mol %.

The 1-butene content is preferably from 5 mol % to 50 mol %. It is morepreferably at least 10 mol %, further preferably at least 15 mol %.Further, it is more preferably at most 40 mol %, further preferably atmost 30 mol %.

The polymer (IA1) may contain a small amount of constituting unitsderived from an α-olefin other than propylene and 1-butene. For example,it may contain at most 10 mol %, more preferably at most 5 mol %, ofethylene.

The polymer (IA1) may be a random copolymer or a block copolymer,preferably a random copolymer, whereby the melting point of thecopolymer can more effectively be lowered. Further, the polymer (IA1)may be straight-chained or branched.

Preferably, the polymer (IA1) is one wherein the molecular weightdistribution Mw/Mn represented by the ratio of the weight averagemolecular weight Mw to the number average molecular weight Mn is at most3.0. This means that the molecular weight distribution is narrow, andthe molecular weight of the copolymer is uniform. By using such apolymer (IA1), control of the particle size becomes easy at the time ofdispersing in water, and there will be a merit such that a resindispersion wherein the dispersed particle sizes are small, the particlesize distribution is narrow and the particles are dispersed stably, canbe obtained. It is more preferably at most 2.5. However, usually, it isat least 1.0. The molecular weight distribution Mw/Mn can be obtained byGPC.

More preferably, the melting point Tm of the polymer (IA1) is preferablyat most 120° C. It is more preferably at most 100° C., furtherpreferably at most 90° C. As the melting point Tm is lower than 120° C.,the crystallinity tends to be low, and the solubility in the solventwill be improved, and the emulsification and dispersion operations tendto be more readily carried out at a low temperature, such beingdesirable. Further, in a case where such a resin dispersion is used inan application as e.g. a coating material or adhesive, it isadvantageous that it melts at a low baking temperature. However, themelting point Tm of the polymer (IA1) is usually at least 35° C.,preferably at least 50° C., more preferably at least 60° C., furtherpreferably at least 65° C., most preferably at least 70° C. It isadvantageous from the viewpoint of high thermal resistance, highhardness and non-tackiness. The melting point Tm can be measured by adifferential scanning calorimeter (DSC).

As a commercial product available as the polymer (IA1), Tafiner XM-7070or XM-7080, manufactured by Mitsui Chemicals, Inc., may, for example, bementioned.

As the polyolefin (A1), one type may be used alone, or two or more typesmay be used in combination.

The method for preparing the propylene polymer (IA1) of the presentinvention is not particularly limited and may be any method so long asit is capable of producing a polymer satisfying the requirements of thepresent invention. For example, radical polymerization, cationicpolymerization, anionic polymerization or coordination polymerizationmay be mentioned, and each may be living polymerization.

In the case of coordination polymerization, a method for polymerizationby a Ziegler Natta catalyst or a method for polymerization by a singlesite catalyst or a Kaminsky catalyst may, for example, be mentioned. Asa preferred method, a production method by means of a single sitecatalyst may be mentioned. As a reason, it may be mentioned that ingeneral, with a single site catalyst, by designing the ligand, themolecular weight distribution or the stereoregularity distribution canbe made sharp. Further, as the single site catalyst, a metallocenecatalyst or a Brookhart type catalyst may, for example, be used. In thecase of the metallocene catalyst, a preferred catalyst may be selecteddepending upon the stereoregularity of the polyolefin to be polymerized,such as C₁ symmetric type, C₂ symmetric type, C_(2V) symmetric type orC_(S) symmetric type. Preferably, a C₁ symmetric type or C₂ symmetrictype metallocene catalyst may be employed.

Further, the polymerization may be of any type such as solutionpolymerization, slurry polymerization, bulk polymerization or gas-phasepolymerization. In the case of solution polymerization or slurrypolymerization, the solvent may, for example, be an aromatic hydrocarbonsuch as toluene or xylene, an aliphatic hydrocarbon such as hexane,octane or decane, an alicyclic aliphatic hydrocarbon such as cyclohexaneor methyl cyclohexane, a halogenated hydrocarbon such as methylenechloride, carbon tetrachloride or chlorobenzene, an ester such as methylacetate, ethyl acetate, propyl acetate or butyl acetate, a ketone suchas acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, an alcohol such as methanol, ethanol, n-propanol,isopropanol or n-butanol, an ether such as dibutyl ether ortetrahydrofuran, or a polar solvent such as dimethylformamide ordimethylsulfoxide. Among them, an aromatic hydrocarbon, an aliphatichydrocarbon or an alicyclic hydrocarbon is preferred, and more preferredis toluene, xylene, hexane, heptane, cyclopentane or cyclohexane. Thesesolvents may be used alone or in combination as a mixture of two or moreof them.

1-2) Propylene Polymer (IA2) Having Reactive Groups

As the propylene polymer (IA2) having reactive groups, a copolymer(IA2a) having an unsaturated compound having no reactive group and anunsaturated compound having a reactive group copolymerized at the timeof polymerization, or a polymer (IA2b) having a radical polymerizableunsaturated compound having a reactive group graft-polymerized to apropylene polymer, may, for example, be used.

The copolymer (IA2a) is a copolymer which is obtainable bycopolymerizing an unsaturated compound having no reactive group with anunsaturated compound having a reactive group and which has theunsaturated compound having the reactive group inserted to the mainchain. For example, it is obtainable by copolymerizing propylene with anα,β-unsaturated carboxylic acid or its anhydride such as an acrylic acidor maleic anhydride. Specifically, as the copolymer (IA2a), apropylene-acrylic acid copolymer, or a propylene-an acrylic acidester-maleic anhydride copolymer, may, for example, be used. Thesecopolymers may be used alone or in combination as a mixture of two ormore of them. As the production method, a method described in (IA1) maybe used in the same manner.

The polymer (IA2b) is obtainable by graft-polymerizing a radicalpolymerizable unsaturated compound having a reactive group to apreliminarily polymerized propylene polymer, wherein the unsaturatedcompound having a reactive group is grafted to the main chain. It is,for example, a polymer obtained by grafting e.g. (meth)acrylic acid,fumaric acid, maleic acid or its anhydride, itaconic acid or itsanhydride, crotonic acid, 2-hydroxyethyl (meth)acrylate or2-hydroxypropyl (meth)acrylate, (meth) acrylamide, (dimethylamino)ethyl(meth)acrylate, glycidyl (meth)acrylate, or (2-isocyanate)ethyl(meth)acrylate, to a propylene polymer such as a polyethylene or apropylene-butene copolymer. These polymers may be used alone or incombination as a mixture of two or more of them. Here, (meth)acrylicacid is a general term for acrylic acid and methacrylic acid, and suchapplies to other similar cases.

As the propylene polymer in this reaction, the above-mentioned propylenepolymer (IA1) having no reactive group may be used.

Specifically, the polymer (IA2b) may, for example, be a maleicanhydride-modified polypropylene or its chlorinated product, a maleicanhydride-modified ethylene-propylene copolymer or its chlorinatedproduct, a maleic anhydride-modified propylene-butene copolymer, anacrylic acid-modified propylene or its chlorinated product, an acrylicacid-modified ethylene-propylene copolymer or its chlorinated product,or an acrylic acid-modified propylene-butene copolymer. These copolymersmay be used alone or in combination as a mixture of two or more of them.

The radical polymerization initiator to be used for the graftpolymerization may be suitably selected for use from usual radicalpolymerization initiators, and for example, an organic peroxide orazonitrile may be mentioned. As the organic peroxide, a peroxyketal suchas di(t-butylperoxy)cyclohexane, a hydroperoxide such as cumenehydroperoxide, a dialkyl peroxide such as di(t-butyl) peroxide, a diacylperoxide such as benzoyl peroxide, or a peroxyester such as t-butylperoxy isopropyl monocarbonate may be used. The azonitrile may, forexample, be azobisbutyronitrile or azobisisopropylnitrile. Among them,benzoyl peroxide or t-butyl peroxy isopropyl monocarbonate isparticularly preferred. These initiators may be used alone or incombination as a mixture of two or more of them.

The ratio of the radical polymerization initiator to the graft copolymerunits to be used is usually within a range of radical polymerizationinitiator:graft copolymer units=1:100 to 2:1 (molar ratio), preferablywithin a range of 1:20 to 1:1.

The process for producing the polymer (A2b) is not particularly limitedand may be any method so long as it is capable of producing a polymersatisfying the requirements of the present invention. For example, asolution modification method (a method of heating and stirring in asolution for the reaction) or a melt modification method (a method ofmelting, heating and stirring in the absence of a solvent, or a methodof heating and kneading by an extruder for the reaction) may bementioned.

As the solvent in the case of production in the solution, the solventmentioned in (1-1) may be used in the same manner.

The reaction temperature is usually at least 50° C., preferably within arange of from 80 to 300° C. More preferably, in the case of the solutionmodification method, the temperature is within a range of from 80 to200° C., and in the case of the melt modification method, thetemperature is within a range of from 150 to 300° C. The reaction timeis usually from about 2 to 20 hours. The reaction time is usually fromabout 2 to 20 hours.

The content of reactive groups in the propylene polymer (IA2a) havingreactive groups is preferably within a range of from 0.01 to 5 mmol per1 g of the propylene polymer i.e. from 0.01 to 5 mol/g. The lower limitvalue is more preferably 0.05 mmol/g, further preferably 0.1 mmol/g,particularly preferably 0.15 mmol/g. The upper limit value is morepreferably 1 mmol/g, further preferably 0.8 mmol/g. As it is higher thanthe lower limit value, the amount of the hydrophilic polymer (IB) bondedincreases, and the hydrophilicity of the polymer (IC) increases, wherebythe dispersed particle sizes tend to be small, and as it is lower thanthe upper limit value, the adhesion to a crystalline propylene polymeras a substrate tends to increase.

Here, the propylene polymer (IA2) may be a straight-chained or branched.

In the present invention, both of the propylene polymer (IA1) having noreactive group and the propylene polymer (IA2) having reactive groupsmay suitably be used depending upon the combination with the hydrophilicpolymer (IB) or the desired properties of the polymer is (IC). However,preferred is the propylene polymer (IA2) having reactive groups. Theamount of the hydrophilic polymer (IB) to be bonded can thereby beeasily controlled, and there is a merit such that various reactions maybe employed for the bonding.

The reactive groups may, for example, be carboxylic acid groups,dicarboxylic anhydride groups, dicarboxylic anhydride monoester groups,hydroxyl groups, amino groups, epoxy groups or isocyanate groups. Morepreferably, the propylene polymer (IA) has carboxylic acid derivativegroups i.e. at least one group selected from the group consisting ofcarboxylic acid groups, dicarboxylic anhydride groups and dicarboxylicanhydride monoester groups. These carboxylic acid groups, etc. arehighly reactive and can easily be bonded to a hydrophilic polymer. Notonly that, there are many unsaturated compounds having such groups,which may easily be copolymerized or graft-polymerized to a propylenepolymer.

In the case of a carboxylic acid derivative group, the content of thereactive group is an amount calculated as a group represented by—C(═O)O—. Namely, a dicarboxylic anhydride group is regarded ascontaining two carboxylic acid groups in the group, and accordingly, 1mol of the dicarboxylic anhydride group is counted as 2 mols of thereactive group.

Either one of the polymer (IA2a) and the polymer (IA2b) may be used.Usually, however, preferred is the polymer (IA2b), since it has a meritsuch that the amount of the hydrophilic polymer (IB) to be bonded caneasily be controlled.

(2) Polymer (IC) Having an Acidic Group Bonded to Propylene Polymer (IA)

One having an acidic group bonded to a propylene polymer (IA) may beused as it is, as the polymer (IC).

The acidic group in the present invention is meant for an electron pairaccepting group and is not particularly limited. For example, acarboxylic acid group (—COOH), a sulfo group (—SO₃H), a sulfino group(—SO₂H) or a phosphono group (—PO₂H) may be mentioned. The carboxylicacid group may be in the state of a dicarboxylic anhydride group(—CO—O—OC—) before being dispersed in water. Among them, a carboxylicacid derivative group i.e. at least one member selected from the groupconsisting of a carboxylic acid group, a dicarboxylic anhydride groupand a dicarboxylic anhydride monoester group, is preferred. Thecarboxylic acid derivative group may, for example, be a (meth)acrylicacid group, a fumaric acid group, a maleic acid group or its anhydridegroup, an itaconic acid group or its anhydride group, or a crotonic acidgroup.

The amount of the acidic group bonded is preferably within a range offrom 0.4 to 5 mmol per 1 g of the propylene polymer (IA), i.e. from 0.4to 5 mmol/g. The more preferred lower limit value is 0.6 mmol/g, afurther preferred lower limit value is 0.8 mmol/g. A more preferredupper limit value is 3 mmol/g, and a further preferred upper limit valueis 1.6 mmol/g. As it is higher than the lower limit value, the polarityof the polymer increases, and the hydrophilicity increases, whereby thedispersed particle sizes tend to be small. As it is lower than the upperlimit value, the adhesion to a crystalline polyolefin as a substratetends to increase. In the case of the carboxylic acid derivative group,the content of the acidic group is an amount calculated as a grouprepresented by —C(═O)O—.

(3) Hydrophilic Polymer (IB)

As the hydrophilic polymer (IB), any one of a synthetic polymer, asemisynthetic polymer and a natural polymer may be employed without anyparticular restriction so long as it does not substantially impair theeffects of the present invention. It may have reactive groups.

The synthetic polymer is not particularly limited, and for example, apoly(meth)acrylic resin, a polyether resin, a polyvinyl alcohol resin ora polyvinyl pyrrolidone resin may, for example, be used. The naturalpolymer is not particularly limited, and for example, a starch such ascorn starch, wheat starch, sweet potato starch, potato starch, tapiocastarch or rice starch, a seaweed such as dried layer, agar or sodiumalginate, a plant mucilage such as gum Arabic, tragacauth gum or konjac,an animal protein such as hide glue, casein or gelatin, or a fermentedmucilage such as pullulan or dextrin may, for example, be used. Thesemisynthetic polymer is not particularly limited, and for example, astarch such as carboxyl starch, cation starch or dextrin, or a cellulosesuch as viscose, methyl cellulose, ethyl cellulose, carboxylmethylcellulose or hydroxyethyl cellulose may, for example, be used.

Among them, preferred is a synthetic polymer whereby the degree ofhydrophilicity can easily be controlled, and the properties arestabilized. More preferred is an acrylic resin such as apoly(meth)acrylic resin, a polyvinyl alcohol resin, a polyvinylpyrrolidone resin or a polyether resin. They may be used alone or incombination as a mixture of two or more of them. A highly hydrophilicpolyether resin is most preferred.

The acrylic resin to be used in the present invention is usuallyobtained by polymerizing an unsaturated carboxylic acid or its ester oranhydride by radical polymerization, anionic polymerization or cationicpolymerization. The method for bonding it with the propylene polymer(IA) is not particularly limited, and for example, a method of carryingout radical polymerization in the presence of a propylene polymer, or amethod of reacting an acrylic resin having a reactive group such as ahydroxyl group, an amino group, a glycidyl group or a carboxylic(anhydride) group with a propylene polymer having a reactive group, may,for example, be mentioned.

The hydrophilic unsaturated carboxylic acid or its ester or anhydridemay preferably be (meth)acrylic acid, hydroxylethyl (meth)acrylate,dimethylaminoethyl (meth)acrylate, a quaternary product ofdimethylaminoethyl (meth)acrylate or (meth) acrylamide.

The polyvinyl alcohol resin to be used in the present invention isobtained usually by polymerizing vinyl acetate to obtain a polyvinylacetate, followed by saponification. The saponification degree may becomplete saponification or partial saponification.

The polyvinyl pyrrolidone resin to be used in the present invention isobtained usually by polymerizing vinyl pyrrolidone.

The polyether resin to be used in the present invention is obtainedusually by subjecting a cyclic alkylene oxide or a cyclic alkylene imineto ring-opening polymerization. The method for bonding it to thepropylene polymer (IA) is not particularly limited, and for example, amethod of subjecting a cyclic alkylene oxide to ring-openingpolymerization in a propylene polymer having reactive groups, or amethod of reacting a hydrophilic polymer having reactive groups such asa polyether polyol or a polyether amine obtained by e.g. ring-openingpolymerization, with a propylene polymer having reactive groups, may,for example, be mentioned.

The polyether amine is a compound having a primary or secondary aminogroup as a reactive group at one terminal or both terminals of a resinhaving a polyether skeleton. As such a polyether amine, Jeffamine Mseries, D series or ED series, manufactured by Huntsman Corporation may,for example, be used. The polyether polyol is a compound having ahydroxyl group as a reactive group at both terminals of a resin having apolyether skeleton.

The polyalkylene oxide or the polyalkylene imine showing hydrophilicitymay, for example, be preferably polyethylene oxide, polypropylene oxideor polyethylene imine.

Before bonding to the propylene polymer (A), the hydrophilic polymer (B)to be used in the present invention preferably has at least one reactivegroup which is reactive thereto. As such a reactive group, a carboxylicacid group, a dicarboxylic anhydride group, a dicarboxylic anhydridemonoester group, a hydroxyl group, an amino group, an epoxy group or anisocyanate group may, for example, be mentioned. Preferably, it has atleast an amino group. The amino group has a high reactivity with variousreactive groups such as a carboxylic acid group, a carboxylic anhydridegroup, a glycidyl group and an isocyanate group, whereby it is easy tobond the hydrophilic polymer to the propylene is polymer. The aminogroup may be primary, secondary or tertiary, but more preferred is aprimary amino group.

At least one reactive group may be present, but more preferably, it hasonly one reactive group. If it has two or more reactive groups, at thetime of bonding it to the propylene polymer (IA), it tends to form athree dimensional network structure and is likely to be geled.

However, it may have a plurality of reactive groups, if a reactive grouphaving a higher reactivity than others is only one. For example, ahydrophilic polymer having a plurality of hydroxyl groups and one aminogroup having a higher reactivity than the hydroxyl groups, is apreferred example. Here, the reactivity is a reactivity with thereactive group of the propylene polymer (IA).

The hydrophilic polymer (IB) in the present invention is required tohave a high molecular weight in order to impart sufficienthydrophilicity to the polymer (IC), and it is one having a weightaverage molecular weight Mw of at least 200, as measured by GPC andcalculated by a calibration curve of polystyrene. The lower limit valueis preferably 300, more preferably 500. However, the weight averagemolecular weight Mw is preferably at most 200,000. The upper limit valueis more preferably 100,000, further preferably 10,000. As Mw is higherthan the lower limit value, the hydrophilicity of the polymer (IC) tendsto increase, and the dispersed particle sizes tend to be small so thatthe dispersion tends to be stabilized, and as it is lower than the upperlimit value, the viscosity tends to be low, and the preparation of theresin dispersion tends to be easy. Here, the GPC measurement is carriedout by a conventional method by using a commercial available apparatusand by using e.g. THF as a solvent.

The amount of the hydrophilic polymer (IB) bonded to the propylenepolymer (IA) is preferably within a range of from 0.01 to 5 mmol per 1 gof the propylene polymer, i.e. from 0.01 to 5 mmol/g. The lower limitvalue is more preferably 0.05 mmol/g, further preferably 0.1 mmol/g,particularly preferably 0.15 mmol/g. The upper limit value is morepreferably 1 mmol/g, further preferably 0.8 mmol/g. As the amount ishigher than the lower limit value, the hydrophilicity of the polymer(IC) tends to increase, and the dispersed particle sizes tend to besmall so that the dispersion tends to be stabilized, and as it is lowerthan the upper limit value, the adhesion to a crystalline propylenepolymer as a substrate tends to increase.

The propylene polymer (IA) and the hydrophilic polymer (IB) may form agraft copolymer having the hydrophilic polymer (IB) graft-bonded to thepropylene polymer (IA), or a block copolymer of the propylene polymer(IA) and the hydrophilic polymer (IB) including such a state that thehydrophilic polymer (IB) is bonded to one end or both ends of thepropylene polymer (IA). However, preferred is a graft copolymer in viewof such merits that the content of the hydrophilic polymer (IB) is easyto control, and as compared with a block copolymer, the content of thehydrophilic polymer (IB) can easily be increased.

Heretofore, there has been a method wherein carboxylic acid groups aregraft-bonded to a propylene polymer chain, and the carboxylic acidgroups are neutralized by a base, followed by dispersion in water.However, according to the method of the present invention wherein thehydrophilic polymer (IB) is graft-bonded to a propylene polymer chain,as compared with the conventional method, the molar amount of the groupsgraft-bonded directly to the propylene polymer chain may besubstantially small to attain dispersion in water. Accordingly, there isa merit such that the adhesion to a polyolefin substrate is made highwithout impairing the nature of the propylene polymer.

The hydrophilic polymer (IB) can be bonded to the propylene polymer (IA)by various reaction modes. Such modes are not particularly limited, and,for example, a radical graft reaction or a reaction utilizing reactivegroups may be mentioned.

According to the radical graft reaction, a bond by a carbon-carbonconjugated bond will be formed.

The reaction utilizing reactive groups is one wherein both of thepropylene polymer (IA) and the hydrophilic polymer (IB) have reactivegroups and bonded by reacting them to form a conjugated bond or an ionicbond. As such a reaction, one mentioned in (2) under “WITH RESPECT TOTHE FIRST EMBODIMENT” may be used in the same manner.

(4) Polymer (IC) Having Hydrophilic Polymer (IB) Bonded to PropylenePolymer (IA)

As a method for producing the polymer (IC) by bonding the hydrophilicpolymer (IB) to the propylene polymer (IA), there is usually a method(IR1) wherein a hydrophilic polymer is polymerized in the presence ofthe propylene polymer (IA) to form the hydrophilic polymer (IB) bondedto the propylene polymer (IA), or a method (IR2) wherein a preliminarilypolymerized hydrophilic polymer (IB) is bonded to the propylene polymer(IA). In either method, as the propylene polymer (IA), either apropylene polymer (IA1) having no reactive group or a propylene polymer(IA2) having reactive groups, may be used.

(4-1) Method (IR1) for Producing Polymer (IC)

In this method, a hydrophilic monomer is polymerized in the presence ofthe propylene polymer (IA) to obtain the hydrophilic polymer (IB) bondedto the propylene polymer (IA). The method for polymerization of thehydrophilic monomer may, for example, be addition polymerization,condensation polymerization or ring-opening polymerization. At thattime, a hydrophobic monomer may be copolymerized, so long as it iswithin a range where a hydrophilic polymer can be formed after thepolymerization.

Specifically, there is, for example, a method wherein a hydrophilicradical polymerizable unsaturated compound is polymerized in thepresence of a radical polymerization initiator to form a hydrophilicpolymer (IB) and at the same time to bond it to the propylene polymer(IA). In such a case, as the propylene polymer (IA), a propylene polymer(IA2) having reactive groups may be used, but usually, a propylenepolymer (IA1) having no reactive group is employed.

The hydrophilic radical polymerizable unsaturated compound is notparticularly limited, and it may, for example, be (meth)acrylic acid,hydroxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate,dimethylaminoethyl (meth)acrylate, quaternary dimethylaminoethyl(meth)acrylate or vinyl pyrrolidone. The copolymerizable hydrophobicmonomer may, for example, be a (meth)acrylic acid ester such as methyl(meth)acrylate or butyl (meth)acrylate, or vinyl acetate.

Otherwise, a radical polymerizable unsaturated compound may bepolymerized in the presence of a radical polymerization initiator toform a polymer and at the same time to bond it to the propylene polymer(IA), followed by modifying it to the hydrophilic polymer (IB). Forexample, a method wherein t-butyl (meth)acrylate is polymerized and thenhydrolyzed under an acidic condition to convert it to apoly(meth)acrylic acid, or a method wherein vinyl acetate is polymerizedand then saponified to modify it to a polyvinyl alcohol, may bementioned. The copolymerizable hydrophobic monomer may, for example, bea (meth)acrylic acid ester such as methyl (meth)acrylate or butyl(meth)acrylate, or vinyl acetate. In such a case, as the propylenepolymer (IA), a propylene polymer (IA2) having reactive groups bondedthereto may be used, but usually, a propylene polymer (IA1) having noreactive group is employed.

Or, there is a method wherein a propylene polymer (IA2) having reactivegroups is employed, and using such reactive groups as initial terminals,a hydrophilic radical polymerizable unsaturated compound, a hydrophilicring-opening polymerization monomer or the like is polymerized to obtaina hydrophilic polymer (IB).

As the hydrophilic radical polymerizable unsaturated compound, theabove-mentioned one may be used in the same manner. The hydrophilicring-opening polymerization monomer may, for example, be ethylene oxide,propylene oxide or ethylene imine. The copolymerizable hydrophobicmonomer may, for example, be trimethylene oxide, tetrahydrofuran,β-propiolactone, γ-butyrolactone or ε-caprolactone.

They may be used alone or in combination as a mixture of two or more ofthem.

The reaction method is not particularly limited so long as a polymersatisfying the requirements of the present invention can thereby beproduced. For example, a method of heating and stirring in a solutionfor the reaction, a method of melting, heating and stirring in theabsence of a solvent for the reaction, or a method of heating andkneading by an extruder for the reaction, may be mentioned. The reactiontemperature is usually within a range of from 0 to 200° C., preferablywithin a range of from 30 to 150° C. As the solvent in the case ofproduction in a solution, the solvent mentioned in (1-1) may be used inthe same manner.

(4-2) Method (IR2) for Producing Polymer (IC)

In this method, a preliminarily polymerized hydrophilic polymer (IB) isbonded to the propylene polymer (IA). In this case, as the hydrophilicpolymer (IB), one mentioned in (3) may be used.

Specifically, there is, for example, a method wherein firstly, at thetime of polymerizing a hydrophilic monomer to form a hydrophilicpolymer, an unsaturated double bond is retained in its molecule, andthen it is graft-polymerized to the propylene polymer (IA) by means of aradical polymerization initiator. In such a case, as the propylenepolymer (IA), a propylene polymer (IA2) having reactive groups may beused, but usually, a propylene polymer (IA1) having no reactive group isused.

Further, there is a method wherein firstly, a hydrophilic polymer havinga reactive group at its terminal is formed by polymerization, and thenthis is bonded to a propylene polymer (IA2) having reactive groups. Thehydrophilic polymer having a reactive group at its terminal may beobtained by polymerizing a hydrophilic monomer by using a compoundhaving a reactive group, as an initiator or a chain transfer agent. Or,it may be obtained by ring-opening polymerization of a hydrophilicring-opening polymerization monomer such as an epoxy compound.

As the hydrophilic monomer which may be used in such a case, varioushydrophilic monomers mentioned in (4-1) may be used in the same manner.

They may be used alone or in combination as a mixture of two or more ofthem.

The reaction method is not particularly limited and may be any method solong as a polymer satisfying the requirements of the present inventioncan thereby be produced. For example, a method of heating and stirringin a solution for the reaction, a method of melting, heating andstirring in the absence of a solvent for the reaction, or a method ofheating and kneading by an extruder for the reaction, may be mentioned.The reaction temperature is usually within a range of from 0 to 200° C.,preferably within a range of from 30 to 150° C. As the solvent in thecase of production in a solution, the solvent mentioned in (1-1) may beused in the same manner.

(5) Aqueous Resin Dispersion

In a case where an aqueous resin dispersion of the polymer (IC) is to beproduced, its production method is not particularly limited, and forexample, a method wherein a solvent other than water is added to theabove polymer (IC), and the polymer is dissolved, if necessary, byheating, followed by addition of water to obtain a dispersion, or amethod wherein the polymer (IC) is melted at a temperature of at leastthe melting temperature, and then, water is added to obtain adispersion, may, for example, be mentioned.

Preferred is the former. By the method which comprises preparing amixture of the polymer, water and a solvent other than water, and then,removing the solvent from the mixture to obtain an aqueous dispersion,an aqueous dispersion with fine particle sizes can easily be prepared.At the time of preparing the mixture, heating may be applied as the caserequires. The temperature is usually from 30 to 150° C. The proportionof the solvent other than water in the resin dispersion is made to beusually at most 50%, finally. It is preferably at most 20%, morepreferably at most 10%, particularly preferably at most 1%.

The solvent other than water to be used in this method may, for example,be an aromatic hydrocarbon such as toluene or xylene, an aliphatichydrocarbon such as hexane, octane or decane, an alicyclic aliphatichydrocarbon such as cyclohexane or methyl cyclohexane, a halogenatedhydrocarbon such as methylene chloride, carbon tetrachloride orchlorobenzene, an ester such as methyl acetate, ethyl acetate, propylacetate or butyl acetate, a ketone such as acetone, methyl ethyl ketone,methyl propyl ketone, methyl isobutyl ketone or cyclohexanone, analcohol such as methanol, ethanol, n-propanol, isopropanol, n-butanol,2-butanol, isobutanol, t-butanol, cyclohexanol, ethylene glycol,propylene glycol or butanediol, an ether such as dipropyl ether, dibutylether or tetrahydrofuran, an organic solvent having two or morefunctional groups, such as 2-methoxyethanol, 2-ethoxyethanol,2-butoxyethanol, 2-methoxypropanol, 2-ethoxypropanol or diacetonealcohol, or a polar solvent such as dimethylformamide ordimethylsulfoxide.

Among them, a solvent soluble in water in an amount of at least 1 wt %is preferred, and more preferred is one soluble in water in an amount ofat least 5 wt %. For example, methyl ethyl ketone, methyl propyl ketone,cyclohexanone, n-propanol, isopropanol, n-butanol, 2-butanol,isobutanol, t-butanol, cyclohexanol, tetrahydrofuran, 2-methoxyethanol,2-ethoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-ethoxypropanol ordiacetone alcohol is preferred.

An apparatus to produce the resin dispersion by adding water afterpreparing a molten state or a state dissolved in a solvent, is notparticularly limited, and for example, a reactor equipped with astirrer, or a single screw or twin screw kneader may be used. Thestirring speed at that time varies to some extent depending upon thechoice of the apparatus, but it is usually within a range of from 10 to1,000 rpm.

The polymer (IC) of the present invention is excellent in dispersibilityin water, whereby the aqueous dispersion of the present invention has amerit such that the dispersed particle sizes are fine, and the resin isdispersed stably. Accordingly, by using such an aqueous dispersion, acoated product having an excellent exterior appearance can be obtained.

In the aqueous resin dispersion of the present invention, the solidcontent based on the entirety is preferably at least 5 wt %, morepreferably at least 10 wt %, further preferably at least 20 wt %.Further, it is preferably at most 70 wt %, more preferably at most 60 wt%, further preferably at most 50 wt %, particularly preferably at most40 wt %. As the amount of the solid content is small, the viscositytends to be low, whereby it is easy to use, as various coating methodsmay be used, and as a dispersion, the stability tends to be high.However, for example, in a case where it is used as a primer or anadhesive, the solid content is preferably high in order to save theenergy and time for drying of water after coating.

(5-1) Resin (ID)

In the resin dispersion of the present invention, particles made of atleast one resin (ID) selected from the group consisting of an acrylicresin, a polyester resin, a polyurethane resin, an epoxy resin and avinyl ester resin, are also dispersed. It may be a resin dispersible bymeans of a surfactant.

The 50% particle diameter of the particles made of the resin (ID) is notparticularly limited so long as it satisfies the above-describedrelation with the 50% particle diameter of the polymer (IC). Inconsideration of the dispersion stability, etc., it is preferably from0.01 μm to 1.0 μm, more preferably from 0.01 μm to 0.5 μm, furtherpreferably from 0.05 μm to 0.5 μm.

Further, in a case where firstly a dispersion containing the particlesmade of the resin (ID) is prepared and then combined with the dispersioncontaining the polymer (IC) particles to obtain the resin dispersion ofthe present invention, the resin solid content in the dispersioncontaining the resin (ID) particles is preferably from 15 to 70 wt %,more preferably from 30 to 60 wt %. The liquid viscosity is preferablyfrom 1 to 50,000 mPa·s, more preferably from 1 to 10,000 mPa·s, furtherpreferably from 10 to 10,000 mPa·s.

Now, the resin (ID) will be described in detail.

(ID-1) Acrylic Resin

The acrylic resin of the present invention is not particularly limitedso long as it is a (meth)acrylic polymer, but, it is meant for ahomopolymer or copolymer of acrylic acid and/or its ester, or ahomopolymer or copolymer of methacrylic acid and/or its ester. Here,(meth)acrylic means acrylic and/or methacrylic.

A specific example of the (meth)acrylic acid ester may, for example, bea (meth)acrylic acid ester monomer having a C₁₋₁₂ alkyl group, such asmethyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate,isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl(meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl(meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate,2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylateor dodecyl (meth)acrylate, or a (meth)acrylic acid ester having a C₆₋₁₂aryl or aralkyl group, such as phenyl (meth)acrylate or benzyl(meth)acrylate.

Or, it may, for example, be a (meth)acrylic acid ester having a C₁₋₂₀alkyl group containing a hetero atom, such as dimethylaminoethyl(meth)acrylate, diethylaminoethyl (meth)acrylate, 2-aminoethyl(meth)acrylate, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate,hydroxybutyl (meth)acrylate, 2-methoxyethyl (meth)acrylate,3-methoxypropyl (meth)acrylate, or an adduct of (meth)acrylic acid and apolyethyleneoxide, a (meth)acrylic acid ester having a C₁₋₂₀ alkyl groupcontaining fluorine atoms, such as trifluoromethyl (meth)acrylate,2-trifluoromethylethyl (meth)acrylate or 2-perfluoroethylethyl(meth)acrylate, or a (meth)acrylamide monomer such as (meth)acrylamideor (meth) acryldimethylamide.

In addition to the above (meth)acrylic acid and/or its esters, oneshaving double bonds at the molecular terminals, so-called macromonomersare included. Such (meth)acrylic macromonomers usually have weightaverage molecular weights within a range of from a few hundreds to50,000. Such a (meth)acrylic oligomer may be used usually within a rangeof from 1 to 80 parts by weight per 100 parts by weight of theabove-mentioned (meth)acrylic acid and/or its esters.

Further, in addition to the above macromonomers, a caprolactone modified(meth)acrylic oligomer, a terminal hydroxyl group-containing(meth)acrylic oligomer, an oligoester (meth)acrylic oligomer, anurethane (meth)acrylate or an epoxy (meth)acrylate may, for example, bementioned.

To the acrylic resin, crosslinkable functional groups may be introducedin order to impart water resistance, heat resistance, solvent resistanceor chemical resistance, and a crosslinking agent may be used incombination. For example, a copolymer having epoxy groups such asglycidyl (meth)acrylate is combined with a polyfunctional carboxylicacid or a polyfunctional amine as a crosslinking agent; a copolymerhaving hydroxyl groups such as 2-hydroxyethyl (meth)acrylate orhydroxybutyl (meth)acrylate is combined with a polyfunctionalisocyanate; or a copolymer having carbonyl groups such as diacetoneacrylamide or acrolein is combined with a crosslinking agent such as apolyfunctional hydrazine such as adipic acid dihydrazide or sebacic aciddihydrazide. Among them, the crosslinking system of the carbonyl groupand the polyfunctional hydrazine is preferred, since it is curable atroom temperature, while it can be stored in the form of one pack system.The amount of such crosslinkable functional groups is preferably atleast 0.5 part by weight, more preferably at least 1 part by weight, per100 parts by weight of the acrylic resin. However, it is preferably atmost 20 parts by weight, more preferably at most 10 parts by weight, per100 parts by weight of the acrylic resin. As it is higher than the lowerlimit value, an adequate crosslinking effect tends to be easilyobtainable, and as it is lower than the upper limit value, the storagestability, etc. tend to increase.

The polymerization method to produce such an acrylic resin is notparticularly limited, and for example, a method such as solutionpolymerization, bulk polymerization emulsion polymerization orsuspension polymerization may be employed.

In order to emulsify in water, an acrylic resin obtained by solutionpolymerization or bulk polymerization to form an aqueous dispersion,emulsification-dispersion may be carried out by a mechanical force ofe.g. a colloid mill in the presence or absence of the solution, and thenthe remaining solvent may be distilled off under reduced pressure oratmospheric pressure, as the case requires. When emulsion polymerizationor suspension polymerization is employed, the polymer can be obtaineddirectly in the form of an aqueous emulsion. A preferred form is anaqueous emulsion obtainable by emulsion polymerization. One available asa commercial product may, for example, be Rikabond manufactured by CSCCo., Ltd. or Acronal manufactured by BASF Japan Ltd.

The acrylic resin of the present invention preferably has a numberaverage molecular weight of at least 1,000, more preferably at least20,000. However, it is preferably at most 1,000,000, more preferably atleast 500,000.

(ID-2) Polyurethane Resin

The polyurethane resin of the present invention is not particularlylimited, and it may, for example, be a urethane polymer obtainable byreacting (i) a component containing an average of at least two activehydrogen atoms in one molecule with (ii) a polyvalent isocyanatecomponent, or a urethane polymer obtainable by reacting an isocyanategroup-containing prepolymer obtainable by reacting the above components(i) and (ii) under an isocyanate group excessive condition, with a chainextender such as a diol. In such urethane polymers, an acid component(an acid residue) may be contained.

Further, the chain extending method for the isocyanate group-containingprepolymer may be carried out by a known method. For example, usingwater, a water-soluble polyamine, a glycol or the like as a chainextender, an isocyanate group-containing prepolymer and the chainextender component may be reacted, if necessary, in the presence of acatalyst.

The component containing an average of at least two active hydrogenatoms in one molecule as the above component (i), is not particularlylimited, but is preferably one having a hydroxyl group-based activehydrogen. The following may be mentioned as specific examples of such acompound.

(1) Diol compound: Ethylene glycol, propylene glycol, diethylene glycol,triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol,2,3-butylene glycol, 1,4-butylene glycol, 1,5-pentandiol, neopentylglycol, 1,6-hexane glycol, 2,5-hexanediol, dipropylene glycol,2,2,4-trimethyl-1,3-pentandiol, tricyclodecanedimethanol,1,4-cyclohexanedimethanol, etc.

(2) Polyether diol: An alkylene oxide adduct of the above diol compound,a ring-opening (co)polymer of an alkylene oxide or cyclic ether (such astetrahydrofuran), for example, a polyethylene glycol, a polypropyleneglycol, an ethylene glycol-propylene glycol (block or random) copolymer,a glycol, a polytetramethylene glycol, a polyhexamethylene glycol, apolyoctamethylene glycol, etc.

(3) Polyesterdiol: One obtained by polycondensation of a dicarboxylicacid (anhydride) such as adipic acid, succinic acid, sebacic acid,glutaric acid, maleic acid, fumaric acid or phthalic acid with a diolcompound such as ethylene glycol, propylene glycol, 1,4-butanediol,1,6-hexanediol, 1,8-octamethylenediol or neopentyl glycol, as mentionedin the above (1) under hydroxyl group-excessive condition. Specifically,an ethylene glycol-adipic acid condensate, a butanediol-adipiccondensate, a hexamethylene glycol-adipic acid condensate, an ethyleneglycol-propylene glycol-adipic acid condensate, or a polylactonediolobtained by ring-opening polymerization of lactone using glycol as aninitiator, may, for example, be exemplified.

(4) Polyetheresterdiol: One obtained by adding an ether group-containingdiol (such as the polyetherdiol or diethylene glycol in the above (2))or a mixture thereof with other glycol, to a dicarboxylic acid(anhydride) as exemplified in the above (3), followed by a reaction withan alkylene oxide, for example, a polytetramethylene glycol-adipic acidcondensate, etc.

(5) Polycarbonatediol: A compound represented by the formulaHO—R—(O—C(O)—O—R)x-OH (wherein R is a C₁₋₁₂ saturated fatty acid diolresidue, x is the number of repeating units of the molecule and usuallyis an integer of from 5 to 50), etc. Such a compound can be obtained byan ester exchange method of reacting a saturated aliphatic diol with asubstituted carbonate (such as diethyl carbonate or diphenyl carbonate)under such a condition that hydroxyl groups would be excessive, or amethod of reacting the above saturated aliphatic diol with phosgene, andif necessary, then, further reacting a saturated aliphatic diol.

The compounds as exemplified in the above (1) to (5) may be used aloneor in combination as a mixture of two or more of them.

As the polyvalent isocyanate component (ii) to be reacted with the abovecomponent (i), an aliphatic, alicyclic or aromatic compound having anaverage of at least two isocyanate groups per molecule may be used.

As the aliphatic diisocyanate compound, a C₁₋₁₂ aliphatic diisocyanateis preferred, and it may, for example, be hexamethylene diisocyanate or2,2,4-trimethylhexane diisocyanate. As the alicyclic diisocyanatecompound, a C₄₋₁₈ alicyclic diisocyanate is preferred, and it may, forexample, be 1,4-cyclohexane diisocyanate or methylcyclohexylenediisocyanate. As the aromatic isocyanate, tolylene diisocyanate,4,4′-diphenylmethane diisocyanate or xylylene diisocyanate may, forexample, be mentioned.

Further, one containing acid residues in an urethane polymer can bedispersed in water without using a surfactant or with a small amount ofa surfactant, whereby water resistance of a coating film is expected tobe improved. The content of acid residues is suitably within a range offrom 25 to 150 (mgKOH/g), preferably from 30 to 100 (mgKOH/g), as anacid value of the urethane polymer. If the acid value is less than 25,the dispersibility in water tends to be inadequate, and it will berequired to use a surfactant in many cases. On the other hand, if theacid value is larger than 150, the water resistance of the coating filmtends to be poor.

As a method for introducing acid groups into an urethane polymer, aconventional method may be used without any particular restriction. Forexample, a method for introducing acid groups is preferred wherein adimethylol alkanoic acid is substituted for some or all of the glycolcomponents mentioned in the above (2) to (4) to have carboxyl groupspreliminarily introduced to a polyether diol, a polyester diol or apolyether ester diol. The dimethylol alkanoic acid to be used here may,for example, be dimethylol acetic acid, dimethylol propionic acid ordimethylol butyric acid. As a commercial product, Hydran or Vondic,manufactured by Dainippon Ink and Chemicals, Incorporated or Superflex,manufactured by Dai-Ichi Kogyo Seiyaku Co., Ltd., may, for example, bementioned.

The urethane resin in the present invention preferably has a numberaverage molecular weight of at least 1,000, more preferably at least20,000. However, the number average molecular weight is preferably atmost 1,000,000, more preferably at most 200,000.

In a case where the aqueous dispersion of the urethane resin of thepresent invention is to be produced, its production method is notparticularly limited, and it can be produced in accordance with theabove-described method for producing the aqueous dispersion of the anacrylic resin.

(ID-3) Polyester Resin

The polyester resin of the present invention is not particularlylimited, and it may, for example, be one obtained by poly-condensing adicarboxylic acid such as adipic acid, succinic acid, sebacic acid,glutaric acid, maleic acid, fumaric acid or phthalic acid, and/or itsanhydride, with a diol compound such as ethylene glycol, propyleneglycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octamethylenediol orneopentyl glycol, or an ether group-containing diol (such aspolyethylene glycol, polypropylene glycol or polytetramethylene glycol).

Specifically, it may, for example, be an ethylene glycol-adipic acidcondensate, a butanediol-adipic acid condensate, a hexamethyleneglycol-succinic acid condensate, ethyleneglycol-propylene-glycol-phthalic acid condensate or a polyethyleneglycol-adipic acid condensate.

An aqueous dispersion of a polyester resin is obtainable by emulsifyingit in water in the presence or absence of a surfactant. The productionmethod is not particularly limited, but it can be produced in accordancewith the above-mentioned method for producing an aqueous dispersion ofan acrylic resin. One available as a commercial product may, forexample, be Vylonal MD-1200 or MD-1245, manufactured by Toyobo Co., Ltd.

The polyester resin of the present invention preferably has a numberaverage molecular weight of at least 1,000, more preferably at least5,000. However, the number average molecular weight is preferably atmost 500,000, more preferably at most 100,000.

(ID-4) Epoxy Resin

The epoxy resin of the present invention is not particularly limited solong as it is a polymer having at least one epoxy group per molecule.For example, it may be a polyvalent glycidyl ether of phenol which canbe produced by reacting a polyhydric phenol with epichlorohydrin in thepresence of an alkali, or an epoxy group-containing polymer obtainableby reacting such a polyvalent glycidyl ether of phenol with theabove-mentioned polyhydric phenol.

The polyhydric phenol which may be used here, may, for example, bebis(4-hydroxyphenyl)-2,2-propane, 4,4′-dihydroxybenzophenone,bis(4-hydroxyphenyl)-1,1-ethane, bis(4-hydroxyphenyl)-1,1-isobutane,bis(4-hydroxy-t-butyl-phenyl)-2,2-propane, bis(2-hydroxynaphthyl)methaneor 1,5-dihydroxynaphthalene.

Instead of such a polyhydric phenol, a hydrogenated compound havinghydrogen added to some or all of double bonds in its phenyl nucleus, maybe used.

Further, as the epoxy resin, a polyglycidyl ether of a phenolic novolacresin, or a polyglycidyl ether of a polyhydric alcohol may also be used.Such a polyhydric alcohol may, for example, be ethylene glycol,diethylene glycol, triethylene glycol, 1,2-propylene glycol,1,4-propylene glycol, 1,5-pentanediol, 1,2,6-hexanetriol, glycerol,bis(4-hydroxycyclohexyl)-2,2-propane or sorbitol.

An aqueous dispersion of an epoxy resin is obtainable by emulsifyingsuch an epoxy resin in water in the presence or absence of a surfactant.The production method is not particularly limited, but it can beproduced in accordance with the above-described method for producing anaqueous dispersion of an acrylic resin.

A typical commercial product may, for example, be Denacol EM150manufactured by Nagase ChemteX Corporation, obtained by forciblyemulsifying by a surfactant (emulsifier) novolac type epoxy resinobtained by adding epichlorohydrin to a phenol novolac resin, Epi-Rez6006W70 or 5003W55, manufactured by Japan Epoxy Resins Co., Ltd. orWEX-5100, manufactured by Tohto Kasei Co., Ltd.

Further, Denacol EM151 or EM103, obtained by forcibly emulsifying, by anemulsifier, a bisphenol type epoxy resin obtained by similarly addingepichlorohydrin to bisphenol, or Epi-Rez 3510W60, 3515W6, 3522W60 or3540WY55, manufactured by Japan Epoxy Resins Co., Ltd., may, forexample, be mentioned.

Further, as an epoxy resin of alkyl type having epichlorohydrin added toa polyol such as sorbitol, pentaerythritol or glycerol, Denacol EX-611,EX-614, EX-411 or EX-313, manufactured by Nagase ChemteX Corporationmay, for example, be mentioned.

The epoxy resin of the present invention preferably has a number averagemolecular weight of at least 1,000, more preferably at least 20,000.However, the number average molecular weight is preferably at most1,000,000, more preferably at most 200,000.

(ID-5) Vinyl Ester Resin

The vinyl ester resin of the present invention is a polymer of vinylester alone, or a copolymer comprising a polymer of a vinyl estermonomer and another radical polymerizable monomer. As such a radicalpolymerizable monomer, ethylene, a (meth)acrylic acid ester, an aromaticvinyl, an unsaturated nitrile, an acrylamide, (meth)acrylic acid or anα,β-unsaturated dicarboxylic acid may, for example, be mentioned.

Further, the vinyl ester monomer may, for example, be vinyl acetate,vinyl propionate, vinyl pivalate, a C₈₋₁₀ vinyl ester of a tertiarycarboxylic acid, or an alkanoic acid vinyl ester such as so-calledVersatic acid vinyl (such as tradename: Veova10, manufactured by ShellChemicals Japan Ltd.) Among them, vinyl acetate is preferred, and as thevinyl ester resin, a homopolymer of vinyl acetate, or an ethylene-vinylacetate copolymer is particularly preferred.

The weight ratio of the ethylene units and the vinyl ester units in thecopolymer is such that per 100 parts by weight of the vinyl ester units,the ethylene units contained in this polymer are preferably within arange of from 5 to 70 parts by weight, more preferably from 10 to 50parts by weight. As the ethylene units are more than 5 parts by weight,the initial adhesion and the water resistance tend to be improved, andas they are less than 70 parts by weight, the adhesive strength tends tobe improved.

An emulsion of the copolymer can be produced usually by emulsionpolymerization of monomers constituting the above ethylene units and thevinyl ester units. An emulsifier to be used for such emulsionpolymerization may, for example, be a water-soluble polymer compoundsuch as hydroxymethyl cellulose or carboxymethyl cellulose, or aprotective colloid such as a partially saponified or completelysaponified polyvinyl acetate emulsifier. In the present invention, sucha partially saponified polyvinyl acetate emulsifier is employed. Amongsuch partially saponified polyvinyl acetate emulsifiers, a partiallysaponified one having an average polymerization degree of from about 100to 3,000 and an average saponification degree of from 80 to 98 mol %, ismore preferred.

As a specific example of the vinyl ester resin emulsion, a commerciallyavailable aqueous emulsion of an ethylene-vinyl ester copolymer, such asSUMIKA flex 400, 401, 305, 455, 500, 510, 700, 751 or 900 (manufacturedby Sumitomo Chemical Co., Ltd.), Panflex OM-4000 or OM-4200(manufactured by Kuraray Co., Ltd.), Polysol EVA AD-2, AD-3, AD-4, AD-5,AD-51, AD-56, AD-59 or P-900 (manufactured by Showa Highpolymer Co.,Ltd.), or DENKA EVA tex #20, #30, #40M, #60, #81 or #82 (manufactured byDenki Kagaku Kogyo Kabushiki Kaisha), may, for example, be used as itis.

(5-2) Surfactant

In the resin dispersion of the present invention, the content of asurfactant is at most 10 parts by weight, per 100 parts by weight of theresin component (the total amount of the polymer (IC) and the resin(ID)). Namely, despite the fact that the dispersed particle sizes of thepolymer (IC) are very small, a surfactant is not substantially containedor contained only in a very small amount. There is thereby a merit suchthat when the resin dispersion is employed as a coating material,bleeding out can be prevented, and a coated product excellent in theexterior appearance can be obtained, and the resin dispersion of thepresent invention can be used as a coating material for the outermostsurface of the coating. Further, it is possible to improve the waterresistance or oil resistance (GH resistance) of the coating, and theobtainable resin dispersion will be excellent in each of the adhesion,water resistance, moisture resistance, oil resistance (GH resistance)and chemical resistance.

The amount of the surfactant should better be small, and the content ofa surfactant in the resin dispersion is preferably at most 5 parts byweight, per 100 parts by weight of the resin component. It is morepreferably at most 3 parts by weight, further preferably at most 2 partsby weight. The surfactant may not be substantially contained. Thesurfactant being not substantially contained means that it is less than1 part by weight per 100 parts by weight of the total amount of theresin component.

As the surfactant, the one mentioned in (5) under “WITH RESPECT TO THEFIRST EMBODIMENT” may be used in the same manner.

(5-3) Addition of Pigment

A pigment (IE) may be added to the resin dispersion of the presentinvention. The aqueous resin dispersion containing a pigment (IE) issuitable as a coating material. With respect to a description of thepigment (IE), the description of the pigment (E) in (5-2) under “WITHRESPECT TO THE FIRST EMBODIMENT” applies.

(5-4) Other Additives

To the resin dispersion of the present invention, an acidic substance orbasic substance, an additive, a hydrophilic organic solvent, etc. may beincorporated, as the case requires. For their description, thedescription in (5) under “WITH RESPECT TO THE FIRST EMBODIMENT” applies.

The aqueous resin dispersion of the present invention is useful as e.g.a primer, a primerless coating material or an adhesive, and it isparticularly useful as a coating material. The coating material is oneto be applied on a surface of an object for coloration, protection orbonding and is a concept including e.g. so-called ink. Such a coatingmaterial is suitable particularly for a polyolefin substrate, especiallyfor a propylene polymer substrate. For example, it is useful as acoating material or primer for automobiles e.g. for the interior orexterior of automobiles, as a coating material for home electronics suchas mobile phones or personal computers, as a coating material forbuilding materials, as a gravure ink, as an offset ink, etc.

(6) Laminate

The resin dispersion of the present invention or a coating materialcontaining it may be coated on a substrate and heated to form a resinlayer thereby to obtain a laminate. Such a resin layer is a layercomprising a polymer (IC) containing a propylene polymer (IA) and atleast one resin (ID) selected from the group consisting of an acrylicresin, a polyester resin, a polyurethane resin, an epoxy resin and anvinyl ester resin in a weight ratio of (IA):(ID)=90:10 to 10:90, whereinthe content of a surfactant is at most 10 parts by weight, per 100 partsby weight of the total amount of the polymer (IC) and the resin (ID).Such a laminate is useful for various applications for e.g. automobiles,home electronics or building materials. The substrate may be a film, asheet, a plate or the like without any particular restriction as to itsshape.

With respect to other descriptions relating to the laminate and thethermoplastic resin-molded product (IF) of the present invention, thedescriptions of the laminate and the thermoplastic resin-molded product(F) in (6) under “WITH RESPECT TO THE FIRST EMBODIMENT” apply.

With Respect to the Third Embodiment

A method for producing an aqueous resin dispersion comprising a modifiedpolyolefin and water of the present invention is one which comprises adissolving step of dissolving the modified polyolefin in a solvent (a)wherein the solubility of water at 20° C. is from 1.0 to 95.0 wt %, anda dispersing step of adding water thereto, followed by dispersing, and adistillation step of distilling off at least the solvent (a).

Namely, after once dissolving the above modified polyolefin in a solventwherein the solubility of water is within a specific range, water isadded for dispersion, and then the solvent is distilled off, whereby itis possible to obtain an aqueous resin dispersion wherein the dispersedparticle sizes are fine, the particle size distribution is narrow, andthe particles are dispersed stably. Further, the solvent used can easilybe recovered, and thus, the method is excellent also from theenvironmental and process aspects.

Now, the modified polyolefin of the third embodiment will be described.

The modified polyolefin of the present invention means a polyolefinmodified by a hydrophilic polymer and/or an acid. Namely, it is apolymer (IIC) having a hydrophilic polymer (IIB) and/or an acidic groupbonded to a polyolefin (IIA). Such a polymer is excellent indispersibility in water, such being desirable.

Now, it will be described in more detail.

(1) Polyolefin (IIA)

With respect to the polyolefin (IIA), the description of the polyolefin(A1) having no reactive group in (1-1) under “WITH RESPECT TO THE FIRSTEMBODIMENT” applies.

(2) Polymer (IIC1) Having Acidic Group Bonded to Polyolefin (IIA)

The acidic group in the present invention is meant for an electron pairaccepting group and is not particularly limited. For example, acarboxylic acid group (—COOH), a sulfo group (—SO₃H), a sulfino group(—SO₂H) or a phosphono group (—PO₂H) may be mentioned. Among them, acarboxylic acid group is preferred. Before being dispersed in water, thecarboxylic acid group may be at least one member selected from the groupconsisting of a carboxylic acid group, a dicarboxylic anhydride group(—CO—O—OC—) and a dicarboxylic anhydride monoester group (hereinaftersuch a group may generally be referred to as a carboxylic acidderivative group). The carboxylic acid group may, for example, be a(meth)acrylic acid group, a fumaric acid group, a maleic acid group orits anhydride group, an itaconic acid group or its anhydride group, or acrotonic acid group.

The amount of the acidic group bonded is preferably within a range offrom 0.4 to 5 mmol per 1 g of the polyolefin (IIA), i.e. from 0.4 to 5mmol/g. The more preferred lower limit value is 0.6 mmol/g, a furtherpreferred lower limit value is 0.8 mmol/g. A more preferred upper limitvalue is 3 mmol/g, and a further preferred upper limit value is 1.6mmol/g. As it is higher than the lower limit value, the polarity of thepolymer (IIC1) increases, and the hydrophilicity increases, whereby thedispersed particle sizes tend to be small. As it is lower than the upperlimit value, the adhesion to a crystalline polyolefin as a substratetends to increase. Here, a dicarboxylic anhydride group can be regardedas containing two carboxylic acid groups in the group, and therefore,one mol of the dicarboxylic anhydride group is counted as two mols of anacidic group (or a reactive group).

With respect to a method for producing the polyolefin polymer (IIC1),the same method as the method for producing the polyolefin (IIA2) havinga reactive group bonded to a polyolefin (IIA), may be used.

(3) Polymer (IIC2) Having Hydrophilic Polymer (IIB) Bonded to Polyolefin(IIA)

The ratio of the polyolefin (IIA) to the hydrophilic polymer (IIB) isusually (IIA):(IIB)=100:5 to 100:500 parts by weight. If the proportionof the hydrophilic polymer (IIB) is smaller than this range, the polymer(IIC2) tends to fail to be well dispersed, and the dispersed particlediameters tend to be large, whereby the particles are likely to beagglomerated or separated. Inversely, if the ratio of the hydrophilicpolymer (IIB) is larger than this range, the adhesion to a polyolefinmolded product tends to be poor.

The method for producing the polymer (IIC2) by bonding the hydrophilicpolymer (IIB) to the polyolefin (IIA), may usually be a method (IIR1)wherein a hydrophilic monomer (IIB) is polymerized in the presence ofthe polyolefin (IIA) to form the hydrophilic polymer (IIB) bonded to thepolyolefin (IIA), or a method (IIR2) wherein a preliminarily polymerizedhydrophilic polymer (IIB) is bonded to the polyolefin (IIA). Eithermethod may suitably be selected for use depending upon the types andcombination of the polyolefin (IIA) and the hydrophilic polymer (IIB),the desired properties of the polymer (IIC), etc. Further, thehydrophilic polymer (IIB) may be bonded directly to the polyolefin(IIA), or using the after-mentioned polymer (IIA2) having a reactivegroup bonded to a polyolefin (IIA), a hydrophilic polymer (IIB) may bebonded thereto.

(3-1) Polyolefin (IIA2) Having Reactive Group Bonded to Polyolefin (IIA)

As the polyolefin (IIA2) having reactive groups, it is possible toemploy, for example, a copolymer (IIA2a) obtained by copolymerizing anunsaturated compound having no reactive group with an unsaturatedcompound having a reactive group at the time of polymerization of apolyolefin, or a polymer (IIA2b) obtained by graft-polymerizing aradical polymerizable unsaturated compound having a reactive group to apolyolefin (IIA), or a polymer (IIA2c) obtained by converting apolyolefin having unsaturated terminal groups to one having groups of anelement of Group 13 to 17.

With respect to descriptions of the polyolefin (IIA2), the copolymer(IIA2a), the polymer (IIA2b) and the polymer (IIA2c), the descriptionsof the polyolefin (A2) having reactive groups in (1-2) under “WITHRESPECT TO THE FIRST EMBODIMENT” apply.

(3-2) Hydrophilic Polymer (IIB)

With respect to descriptions of the hydrophilic polymer (IIB), thedescriptions of the hydrophilic polymer (B) in (2) under “WITH RESPECTTO THE FIRST EMBODIMENT” apply.

(3-3) Method for Producing Polymer (IIC2)

The method for producing the polymer (IIC2) by bonding the hydrophilicpolymer (IIB) to the polyolefin (IIA) may usually be a method (IIR1) ofpolymerizing a hydrophilic monomer in the presence of a polyolefin toform the hydrophilic polymer (IIB) bonded to the polyolefin, or a method(IIR2) of bonding a preliminarily polymerized hydrophilic polymer (IIB)to a polyolefin.

With respect to a description of the method (IIR1) for producing thepolymer (IIC2), the description of the method (R1) for producing thepolymer (C) in (3-1) under “WITH RESPECT TO THE FIRST EMBODIMENT”applies. With respect to a description of the method (IIR2) forproducing the polymer (IIC2), the description of the method (R2) forproducing the polymer (C) in (3-2) under “WITH RESPECT TO THE FIRSTEMBODIMENT” applies.

(4) Process for Producing Aqueous Resin Dispersion of ModifiedPolyolefin (polymer (IIC))

The method for producing an aqueous resin dispersion of the presentinvention comprises a dissolving step of dissolving the above-mentionedmodified polyolefin (the polymer (IIC)) in a solvent (a) wherein thesolubility of water at 20° C. is from 1.0 to 95.0 wt %, a dispersingstep of adding water thereto, followed by dispersing and a distillationstep of distilling off at least the solvent (a).

The solubility of water in a certain solvent is the amount of watersoluble in the solvent to saturation in the mutual solubility of thesolvent and water and is represented by the content of water in 100 g ofa solution wherein the water is dissolved in the solvent to itssaturation. As a method for measuring the solubility of water, it is,for example, possible to use the method disclosed in e.g. Solvents Guide(compiled by C. Marsden, Cleaver Hume Press Ltd., London (1963), p. 73).

Reference may conveniently be made to “4th Edition, ExperimentalChemistry Lecture 1, Basic Operation 1, compiled by Japan ChemicalSociety, published by Maruzen” p. 153. Water and a solvent arethoroughly mixed at 20° C., and when saturation is reached, the mixtureis left to stand still until the two phases are completely separated,whereupon the upper phase or the lower phase is sampled by e.g. apipette and quantified by e.g. gas chromatography.

The solvent (a) has a solubility of water at 20° C. of from 1.0 to 95.0wt %. If the solubility of water is less than 1.0 wt %, water being apoor solvent for the modified polyolefin will not penetrate into thesolvent (a) which is a good solvent, whereby the polyolefin will notform fine particles. The solubility is preferably at least 3.0 wt %,more preferably at least 5.0 wt %.

On the other hand, if the solubility of water exceeds 95.0 wt %, theliquid-liquid separation from the water after distillation together withthe water tends to be inadequate. It is preferably at most 70.0 wt %,more preferably at most 50.0 wt %, further preferably at most 40.0 wt %,most preferably at most 30.0 wt %.

The solvent having such a proper solubility of water is preferably atleast one member selected from the group consisting of an alcohol, aketone and an ester. An alcohol, a ketone or an ester not only has aproper solubility of water, but also is stable with a reactivity not sohigh as an amine solvent and without forming an oxide like an ethersolvent, and is usually inexpensive.

For example, the alcohol may be 1-pentanol (7.0 wt %), cyclohexanol(11.0 wt %), isobutanol (16.0 wt %), n-butanol (20.0 wt %) or 2-butanol(44.0 wt %). The ketone may, for example, be methyl propyl ketone (3.3wt %), cyclohexanone (9.5 wt %) or methyl ethyl ketone (10.4 wt %). Theester may, for example, be butyl acetate (1.9 wt %), propyl acetate (2.9wt %), ethyl acetate (2.9 wt %) or methyl acetate (8.0 wt %). Here, inthe brackets, the solubilities in water at 20° C. are indicated (source:Solvent Handbook (Kodansha) published in 1976).

These solvents may be used alone as the solvent (a).

One having two or more solvents mixed may be used as the solvent (a). Insuch a case, it is only required that the solubility of water at 20° C.after the mixing is within the above-mentioned range. For example,aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons,halogenated hydrocarbons, esters, ketones, etc. may optionally be mixedand used within such a range.

However, in consideration of the recovery after the distillation,efficiency for reuse, etc., it is preferred to use a single type ofsolvent as the solvent (a).

The amount of the solvent (a) to be used is preferably such that theconcentration after dissolving the polyolefin is within a range of from5 to 50 wt %. In consideration of the efficiency for use of the solvent,the amount of the solvent (a) is preferably not too much to the amountof the modified polyolefin and preferably at least 5 wt %. It is morepreferably at least 10 wt %. On the other hand, it is preferably at most50 wt % so that the viscosity of the solution is not too high, anduniform stirring can be carried out to obtain a uniform dispersion. Itis more preferably at most 40 wt %.

After the dissolution step of dissolving the modified polyolefin in sucha solvent (a), a dispersing step of adding water thereto for dispersion,is carried out. During the dissolution and dispersion, heating may becarried out as the case requires.

The dissolving step and/or the dispersing step is usually preferablycarried out within a temperature range of from 20° C. to 150° C. Ingeneral, the higher the temperature, the easier the dissolution anddispersion. The temperature is more preferably at least 40° C. However,if the solvent to be used has a low boiling point, evaporation is likelyto proceed. Therefore, the temperature is more preferably at most 100°C., further preferably at most 80° C.

The dissolving step and/or the dispersing step is usually preferablycarried out under a pressure of at most 1 MPa. The pressure is morepreferably at most 0.5 MPa, further preferably at most 0.2 MPa. However,the pressure is usually at least 0.01 MPa. Most preferably, it is about0.101 MPa. In general, the dissolution or dispersion can easily becarried out at a high temperature under a high pressure, but it isrequired to use an expensive apparatus durable at a high temperatureunder a high pressure, and a large energy will be required for such ahigh temperature under a high pressure. According to the method forproducing the aqueous resin dispersion of the present invention, it isnot required to set the pressure high, and dispersion of the resin caneasily be carried out, whereby no expensive apparatus is required, andno large energy will be required, such being very advantageous from theviewpoint of the production process.

The amount of water to be added in the dispersing step may varydepending also on the boiling point of the solvent (a), but usually, itis within a range of the solvent (a): water=5:95 to 95:5 by weightratio. The speed for adding water is preferably such that to 100 g of asolution of the modified polyolefin in the solvent (a), 100 g of wateris preferably added over a period of from about 0.01 hour to 10 hours.The method for addition is not particularly limited, but usually wateris dropwise added.

Then, the solvent (a) will be distilled off from the mixture comprisingthe modified polyolefin, the solvent (a) and water. The pressure at thattime is not particularly limited and is usually under reduced pressure,preferably within a range of from 0.101 MPa to 0.001 MPa, although itdepends also on the boiling point of the solvent (a) or the temperatureof the dispersion. At that time, usually, a part of water will also bedistilled.

The amount of the solvent (a) in the aqueous resin dispersion afterdistilling the solvent (a) off, is usually at most 10 wt. %. It ispreferably at most 5 wt %, further preferably at most 2 wt %.

The following (x), (y) or (z) is conceivable as the order of addition ofwater and distillation of the solvent (a), and any one of such methodsmay be employed.

(x) Water is added in its entire amount, followed by the distillation.

(y) After adding water partly, a part of the solvent (a) is distilledoff. This operation is carried out repeatedly.

(z) While water is added, the solvent (a) is continuously distilled off.

(5) Aqueous Resin Dispersion

By the method for producing an aqueous resin dispersion of the presentinvention, it is possible to obtain a dispersion wherein the dispersedparticle sizes are fine, and the particle size distribution is narrow.Further, this dispersion is excellent also in the dispersion stability.

The dispersed particle sizes of the resin (modified polyolefin) in theaqueous resin dispersion obtained by the present invention is usuallysuch that the 50% particle diameter is at most 10 μm, preferably at most1 μm. According to the present invention, the 50% particle diameter canbe made to be at most 0.5 μm, more preferably at most 0.3 μm, furtherpreferably at most 0.2 μm, most preferably at most 0.1 μm. When the 90%particle diameter is likewise obtained, the 90% particle diameter isfurther preferably at most 1 μm, particularly preferably at most 0.5 μm.By making the dispersed particle sizes to be small, it is possible toimprove the dispersion stability, to prevent agglomeration and todisperse the particles more stably. Further, the ratio of the 90%particle diameter to the 50% particle diameter being made to be small,means that the particle size distribution becomes narrow, andconsequently, the dispersion stability will be improved.

The amount of the solid content in the entire aqueous resin dispersionobtained by the present invention is preferably at least 5 wt %, morepreferably at least 10 wt %, further preferably at least 20 wt %.Further, it is preferably at most 70 wt %, more preferably at most 60 wt%, further preferably at most 50 wt, particularly preferably at most 40wt %. As the amount of the solid content is small, the viscosity tendsto be low, and the dispersion can easily be used as applicable tovarious coating methods, and the stability tends to be high as adispersant. However, at the time of using the dispersion as a primer oran adhesive, the solid content should better be high to save the energyand time in drying water after the coating.

To the resin dispersion of the present invention, an aqueous resin or aresin dispersible in water may be mixed for use, as the case requires,within a range not to substantially impair the effects of the presentinvention. For example, it is thereby possible to improve variousphysical properties or adhesion to a substrate film, specifically toimprove the exterior appearance of the coating (glazing or delustering),to reduce the tackiness or to improve the strength, water resistance,weather resistance, abrasion resistance or solvent resistance of thecoating film. For example, a resin mentioned as the hydrophilic polymer(IIB) may be used. The resin dispersible in water may, for example, bean acrylic resin, a polyepoxy resin, a polyester resin, a polyurethaneresin, a melamine resin or an alkyd resin. After mixing such a resin tothe modified polyolefin, the mixture can be made into a dispersion bymeans of the method of the present invention.

According to the production method of the present invention, theobtainable resin dispersion can be made so that the content of thesurfactant is usually at most 15 parts by weight per 100 parts by weightof the polymer (IIC). Namely, the dispersed particle sizes of the resinare very small, and a surfactant is not substantially contained, orcontained only in a very small amount. Heretofore, particularly in thecase of an aqueous resin dispersion, if a surfactant is not used in alarge amount, there has been a problem that a stabilized dispersionwherein the dispersed particle sizes are fine, can hardly be obtainable.Whereas, according to the method of the present invention, it ispossible to obtain a dispersion excellent in the dispersibility asmentioned above, whereby it is not required to use a surfactant in alarge amount. There is thereby a merit such that when the resindispersion is employed as a coating material, bleeding out can beprevented, and a coated product excellent in the exterior appearance canbe obtained, and the resin dispersion of the present invention can beused as a coating material for the outermost surface of the coating.Further, it is possible to improve the water resistance or oilresistance (GH resistance) of the coating, and the obtainable resindispersion will be excellent in each of the adhesion, water resistance,moisture resistance, oil resistance (GH resistance) and chemicalresistance.

The amount of the surfactant should better be small, and the content ofa surfactant in the resin dispersion is preferably at most 10 parts byweight, per 100 parts by weight of the polymer (IIC). It is morepreferably at most 5 parts by weight, further preferably at most 2 partsby weight. The surfactant may not be substantially contained. Thesurfactant being not substantially contained means that it is less than1 part by weight per 100 parts by weight of the polymer (IIC). As thesurfactant, the one mentioned in (5) under “WITH RESPECT TO THE FIRSTEMBODIMENT” may, for example be used.

To the resin dispersion obtainable by the method of the presentinvention, an acidic substance or basic substance, an additive, ahydrophilic organic solvent, etc., may be incorporated as the caserequires. With respect to their description, the description in (5)under “WITH RESPECT TO THE FIRST EMBODIMENT” applies.

The resin dispersion obtainable by the method of the present inventionmay be coated as a coating material on a substrate and heated to form aresin layer thereby to obtain a laminate. The substrate may be a film,sheet, plate or the like without any particularly restriction as to itsshape. Such a laminate is useful for various applications for e.g.automobiles, home electronics or building materials.

With Respect to the Fourth Embodiment

A method for producing a resin dispersion comprising a modifiedpolyolefin and water according to the fourth embodiment of the presentinvention is one which comprises a dispersing step of adding, to asolution having a modified polyolefin dissolved in a solvent (a1)wherein the solubility of water at 20° C. is less than 1.0 wt %, waterand a solvent (a2) wherein the solubility of water at 20° C. is at least1.0%, followed by dispersing, and a distillation step of distilling offat least the solvents (a1) and (a2).

Namely, the above modified polyolefin is preliminarily dissolved in asolvent (a1) having a low water solubility, and then, a solvent (a2)having a high solubility in water, and water were added thereto, and themodified polyolefin is dispersed, and then, the solvents (a1) and (a2)are distilled off, whereby it is possible to obtain an aqueous resindispersion wherein the dispersed particle sizes are fine, the particlesize distribution is narrow, and the particles are dispersed stably.

The modified polyolefin of the present invention means a polyolefinhaving a hydrophilic polymer and/or an acid bonded thereto, i.e. apolyolefin modified by the hydrophilic polymer and/or the acid. Such apolymer is excellent in dispersibility in water, such being desirable.

By the way, a polyolefin has a high hydrophobicity, and accordingly,also as a solvent for the modification step, a solvent having a lowwater solubility such as the solvent (a1) may be employed. Namely, asthe solvent (a1), the solvent used in the modifying step of thepolyolefin may be used as it is. Therefore, after the completion of themodification step, it is not required to remove the solvent or to carryout evaporation to dryness, and it is possible to carry out thedispersing process in the state of the solution having the modified ispolyolefin dissolved in the solvent. Accordingly, the production stepscan be substantially simplified.

With respect to a description of the modified polyolefin, thedescription in (1) to (3) under “WITH RESPECT TO THE THIRD EMBODIMENT”applies.

(4) Method for Producing an Aqueous Resin Dispersion of ModifiedPolyolefin (Polymer (IIC))

The method for producing an aqueous resin dispersion of the presentinvention comprises a dispersing step of adding, to a solution having amodified polyolefin dissolved in a solvent (a1) wherein the solubilityof water at 20° C. is less than 1.0 wt %, water and a solvent (a2)wherein the solubility of water at 20° C. is at least 1.0 wt %, followedby dispersing, and a distillation step of distilling off at least thesolvents (a1) and (a2).

The solvent (a1) has a solubility of water at 20° C. of less than 1.0 wt%. If the solubility of water is 1.0 wt % or higher, the solubility ofthe polyolefin tends to be poor, and it tends to be difficult to be usedas a solvent at the time of modification or polymerization of thepolyolefin. The solubility of water is preferably at most 0.8 wt %, morepreferably at most 0.5 wt %, further preferably at most 0.3 wt %. Thereis no particularly lower limit value for the solubility of water.However, in view of the purpose of the present invention, it is requiredto be a solvent capable of dissolving a polyolefin or its modifiedpolyolefin.

As a solvent having such a solubility of water, a hydrocarbon solventwhich may be halogenated, may be preferably mentioned. Specifically, atleast one member selected from the group consisting of an aromatichydrocarbon, an aliphatic hydrocarbon and a halogenated hydrocarbon maybe mentioned.

For example, the aromatic hydrocarbon may, for example, be toluene orxylene. The aliphatic hydrocarbon includes both of a chain type and acyclic type and may, for example, be hexane, octane, decane, cyclohexaneor methylcyclohexane. The halogenated hydrocarbon may, for example, bemethylene chloride, carbon tetrachloride or chlorobenzene.

These solvents may be used alone as the solvent (a1). From theenvironment viewpoint, a hydrocarbon solvent containing no halogen ismore preferred.

The solvent (a2) has a solubility of water at 20° C. of at least 1.0 wt%. If the solubility of water is less than 1.0 wt %, water being a poorsolvent for the modified polyolefin will not penetrate into the solvent(a), and the polyolefin will not form fine particles. It is preferablyat least 20.0 wt %, more preferably at least 50.0 wt %, furtherpreferably at least 80.0 wt %, still more preferably completely miscible(the solubility of water is infinite).

As a solvent having such a proper solubility of water, at least onemember selected from the group consisting of a ketone, an alcohol and anether may be mentioned.

For example, the ketone may be acetone (infinite), methyl ethyl ketone(10.4 wt %), methyl propyl ketone (3.3 wt) or cyclohexanone (9.5 wt %).The alcohol may, for example, be methanol (infinite), ethanol(infinite), n-propanol (infinite), isopropanol (infinite), n-butanol (20wt %), 2-butanol (44 wt %), isobutanol (16 wt %), 1-pentanol (7 wt %),cyclohexanol (11 wt %), ethylene glycol (infinite), 1,2-propylene glycol(infinite), 1,3-propylene glycol (infinite), 2-methoxyethanol(infinite), 2-ethoxyethanol (infinite), 2-butoxyethanol (infinite),2-methoxypropanol (infinite), 2-ethoxypropanol (infinite) or diacetonealcohol (infinite). The ether may, for example, be tetrahydrofuran(infinite). Here, in the brackets, the solubility in water at 20° C. isindicated (source: Solvent Handbook (Kodansha) published in 1976).

These solvents may be used alone as the solvent (a2).

The boiling point of the solvent (a2) is preferably lower than water.Namely, the boiling point is lower than 100° C. It may thereby readilybe removed by distillation after dispersing. The boiling point ispreferably at most 95° C., more preferably at most 90° C. Specifically,n-propanol, isopropanol, 2-butanol, acetone or methyl ethyl ketone may,for example, be mentioned.

One having two or more solvents mixed, may be used as the solvent (a1)or (a2). In such a case, it is required only that the solubility ofwater at 20° C. after the mixing is within the above range. However, inconsideration of efficiency in recovery and reuse after thedistillation, it is preferred to use one type of a solvent alone as thesolvent (a1) or (a2).

The amount of the solvent (a1) to be used, is preferably such that theconcentration after dissolving the modified polyolefin is within a rangeof from 5 to 60 wt %. When the efficiency in use of the solvent is takeninto consideration, it is desired that the solvent (a1) is not too muchrelative to the amount of the modified polyolefin, and it is preferablyat least 5 wt %, more preferably at least 10 wt %. On the other hand, inorder that the viscosity of the solution is not too high, and uniformstirring can be carried out to obtain a uniform dispersion, it ispreferably at most 60 wt %, more preferably at most 50 wt %.

The modified polyolefin is preliminarily dissolved in such a solvent(a1). During the dissolution, heating may be carried out as the caserequires, and the temperature is usually within a range of from 20° C.to 150° C. Further, the dissolution is carried out usually under apressure of at most 1 MPa, most preferably about 0.101 MPa. However, thepressure is usually at least 0.01 MPa.

Then, a dispersing step of adding a solvent (a2) and water to thissolution, followed by dispersing, is carried out. Also during thedispersing, heating may be carried out as the case requires. Thedispersing step is preferably carried out usually within a temperaturerange of from 20° C. to 150° C. In general, the higher the temperature,the easier the dispersing. It is more preferably at least 40° C.However, if the solvent to be used has a low boiling point, evaporationis likely to proceed and accordingly, it is more preferably at most 100°C., further preferably at most 80° C.

Further, the dispersing step is usually preferably carried out under apressure of at most 1 MPa, more preferably at most 0.5 MPa, furtherpreferably at most 0.2 MPa. However, the pressure is usually at least0.01 MPa, most preferably about 0.101 MPa. In general, the dispersingcan easily be carried out at a high temperature under a high pressure,but it is required to use an expensive apparatus durable at a hightemperature under a high pressure, and a large energy will be requiredfor such a high temperature under a high pressure. According to themethod for producing the aqueous resin dispersion of the presentinvention, it is not required to set the pressure high, and dispersingof the resin can easily be carried out, whereby no expensive apparatusis required, and no large energy will be required, such being veryadvantageous from the viewpoint of the production process.

The amounts of the solvent (a2) and water to be added in the dispersingstep may vary depending also on the boiling point of the solvent (a) andthe solvent (a2), but usually, it is within a range of the (solvent(a)):(solvent (a2)+water)=5:95 to 95:5, preferably 10:90 to 50:50, byweight ratio. Further, the amounts of the solvent (a2) and water areusually within a range of (a2): water=5:95 to 95:5, preferably 20:80 to80:20, by weight ratio.

At the time of carrying out the distillation step, the compositionalfraction of the solvent (a1) is preferably smaller than thecompositional fraction of the solvent (a1) at the azeotropic point ofthe solvent (a1), the solvent (a2) and water.

Namely, the solvent (a1) is thereby preferentially distilled off,whereby an aqueous resin dispersion can easily be produced.

The speed for the addition of water and the solvent (a2) is preferablysuch that when the total of water and the solvent (a2) is 100 g per 100g of the solution of the modified polyolefin in the solvent (a1), theyare added over a period of from about 0.01 hour to 10 hours. The methodfor the addition is not particularly limited, but usually, they aredropwise added.

Then, the solvent (a1) and the solvent (a2) are distilled off from themixture of the modified polyolefin, the solvent (a1), the solvent (a2)and water. The pressure at that time is not particularly limited and isusually under reduced pressure, preferably within a range of from 0.101MPa to 0.001 MPa, although it may depend on the boiling points of thesolvent (a1) and the solvent (a2) or the temperature of the dispersion.At that time, usually, a part of water will also be distilled off.

After the distillation of the solvent (a1) and the solvent (a2), thetotal amount of the solvent (a1) and the solvent (a2) in the aqueousresin dispersion is usually at most 10 wt %, preferably at most 5 wt %,more preferably at most 2 wt %.

The following (x), (y) or (z) is conceivable as the order of addition ofwater and distillation of the solvent (a1) and the solvent (a2), andeither method may be employed.

(x) After adding the entire amount of water and the solvent (a2),distillation of the solvent (a1) and the solvent (a2) is carried out.

(y) After adding water and the solvent (a2) partly, the part of thesolvent (a1) and the solvent (a2) are partly distilled off. Thisoperation is carried out repeatedly.

(z) While water and the solvent (a2) are added, the solvent (a1) and thesolvent (a2) are continuously distilled off.

Whereas, the modified polyolefin of the present invention is usuallyproduced by the following process steps.

Firstly, by a polymerization step, a polyolefin is obtained by theabove-described polymerization reaction of an olefin monomer, and then,by a modifying step of reacting and bonding an acid and/or hydrophilicpolymer to the polyolefin, a modified polyolefin is obtained. Usually,firstly, a first modifying step of bonding an acid to the polyolefin iscarried out to obtain an acid-modified polyolefin, and if necessary, asecond modifying step of further bonding a hydrophilic polymer, iscarried out to obtain a hydrophilic polymer-modified polyolefin.

In the present invention, as a solvent for these steps, it is preferredto employ the solvent (a1). Namely, the modifying step is carried out inthe above solvent (a1). The reaction solution after the modifying stepis a solution having the modified polyolefin dissolved in the solvent(a1), and it may be used as it is in the dispersing step. By using thesame solvent throughout many process steps, it is not required to repeatconcentration to dryness, purification and dissolution for every step,and the process can be simplified, such being very advantageous frommany aspects such as the cost aspect, environmental aspect, etc. Morepreferably, the polymerization step is also carried out in the abovesolvent (a1).

The method for producing an aqueous resin dispersion of the presentinvention preferably further contains a washing step of washing thesolution having the modified polyolefin dissolved in the solvent (a1)obtained as a reaction solution after the modifying step, with a solvent(a3) having a solubility in the solvent (a1) at 20° C. of less than 1.0wt %. The washing step and the process relating thereto will bedescribed in detail in (5).

(5) Method for Producing Modified Polyolefin Solution

The method for producing a modified polyolefin solution of the presentinvention is one wherein after the modifying step of subjecting apolyolefin to a modification reaction in a solvent (b1) to obtain asolution containing a modified polyolefin, a washing step is carried outto wash this solution with a solvent (b2) having a solubility at 20° C.in the solvent (b1) of less than 1.0 wt %.

Namely, washing is carried out with the solvent (b2) which is a poorsolvent to the solvent (b1).

The solvent (b1) is not particularly limited so long as it is a solventwhich is capable of dissolving both a polyolefin and a modifiedpolyolefin and which is capable of carrying out the modifying reaction.However, preferred from the viewpoint of the solubility and thereactivity is a hydrocarbon solvent which may be halogenated.Specifically, at least one member selected from the group consisting ofan aromatic hydrocarbon, an aliphatic hydrocarbon and a halogenatedhydrocarbon may be mentioned. The aromatic hydrocarbon may, for example,be toluene or xylene. The aliphatic hydrocarbon includes both of a chaintype and a cyclic type and may, for example, be hexane, octane, decane,cyclohexane or methylcyclohexane. The halogenated hydrocarbon may, forexample, be methylene chloride, carbon tetrachloride or chlorobenzene.

The solvent (b2) is not particularly limited so long as the solubilityat 20° C. in the solvent (b1) is less than 1.0 wt % and it is capable ofextracting and removing impurities (such as unreacted substances orby-products) in the above solution, and it may, for example, be water oran alcohol. However, preferred is water.

In the washing method, usually, the solvent (b2) is firstly added to asolution of the modified polyolefin in the solvent (b1), followed bystirring or shaking, then the mixture is left to stand to have thesolvent (b1) layer and the solvent (b2) layer separated, whereupon thesolvent (b2) layer is withdrawn. When this cycle is taken as one cycle,this is carried out at least once. By repeating it a few times, theremoval rate of impurities can be increased. The number of repetition isnot particularly limited, so long as the impurities can sufficiently beremoved, but it is usually up to about 30 times.

The amount of the solvent (b2) to be used for washing once is notparticularly limited, but it is usually from about 1/10 to about 10times, by weight ratio, to the solvent (b1).

The time for the stirring or shaking is also not particularly limited,but it is usually from about one minute to about 10 hours.

The temperature of the solvent (b2) at the time of the washing maydepend on the boiling points of the solvents (b1) and (b2), but it isusually from 5 to 90° C. In order to increase the performance forextraction and removal of impurities, the temperature is preferablyhigher than 5° C., more preferably at least 15° C., further preferablyat least 25° C., particularly preferably at least 35° C. On the otherhand, in order to prevent deterioration of the modified polyolefin or toincrease the operation efficiency, the temperature is preferably lowerthan 90° C., more preferably at most 80° C., further preferably at most70° C.

In a case where water is used as the solvent (b2), after the washingstep, it is preferred to carry out a dehydration step to remove water asfar as possible from the solution. The dehydration method is notparticularly limited, and for example, a Dean-Stark dehydrationapparatus or the like may be employed.

As the modifying step of a polyolefin, the modifying step of reactingand bonding an acid and/or a hydrophilic polymer to a polyolefin asdescribed in (2) and (3) may is be mentioned.

For example, firstly, a first modifying step of reacting a polyolefinwith an acid to bond an acidic group thereby to obtain an acid-modifiedpolyolefin, is carried out, and if necessary, a second modifying step offurther bonding a hydrophilic polymer to obtain a hydrophilicpolymer-modified polyolefin is carried out.

As the acidic group, one mentioned in (2) may be used, but it ispreferably a carboxylic acid group, and particularly preferred is adicarboxylic anhydride group (—CO—O—OC—) which has a high reactivity.Namely, a polyolefin is reacted with a dicarboxylic anhydride to obtaina solution containing a polyolefin having dicarboxylic anhydride groupsbonded thereto.

As the hydrophilic polymer, one mentioned in (3) may be employed. In acase where only the first modifying step is carried out, the washingstep will be carried out thereafter.

In a case where both the first modifying step and the second modifyingstep are carried out, the washing step may be carried out after eitherone of them, or may be carried out after each of them. Preferably, thewashing step is carried out at least after the first modifying step,whereby an influence of impurities to the second modifying step can bereduced.

In a case where after obtaining a solution containing a polyolefinhaving dicarboxylic anhydride is groups bonded thereto in the firstmodifying step, a second modifying step is carried out via a washingstep, if water remains in the solution after the washing step, it mayimpair the ring closure of the dicarboxylic anhydride groups, wherebythe reactivity with the hydrophilic polymer in the second modifying stepmay decrease. Accordingly, it is advisable that after the washing step,a dehydration step is carried out to sufficiently ring-close thedicarboxylic anhydride groups, whereupon the second modifying step iscarried out.

Heretofore, as the washing step, a method has been common wherein areaction solution after the modifying step of the polyolefin isconcentrated to dryness, then dissolved in e.g. acetone, and thenreprecipitation is repeated to carry out purification. Whereas,according to the present invention, the reaction solution is subjectedto the above-described washing as it is, whereby it is not necessary torepeat concentration to dryness, purification and dissolution, and theprocess can be simplified, such being very advantageous from manyaspects such as the cost aspect, the environmental aspect, etc.

(6) Aqueous Resin Dispersion

With respect to a description relating to the aqueous resin dispersionobtainable by the method of the present invention, the description in(5) under “WITH RESPECT TO THE THIRD EMBODIMENT” applies.

EXAMPLES

Now, the present invention will be described in further detail withreference to Examples, but it should be understood that the presentinvention is by no means restricted to the following Examples.

Methods for Measuring and Evaluating Physical Properties (1)Stereoregularity (1-1) Stereoregularity of Polypropylene

The stereoregularity (mmmm) of a polypropylene was measured by a ¹³C-NMRspectrum measuring method by means of an NMR apparatus (manufactured byJEOL Ltd., 400 MHz). A sample of from 350 to 500 mg, was completelydissolved by using about 2.2 ml of o-dichlorobenzene in an NMR sampletube of 10 mm in diameter. Then, as a lock solvent, about 0.2 ml ofdeuterated benzene was added and homogenized, and then, measurement wascarried out by a proton complete decoupling method at 130° C. Themeasurement conditions were such that the flip angle was 90°, and thepulse interval was at least 5T₁ (T₁ is a longest value in thespin-lattice relaxation time of a methyl group). In a propylene polymer,the spin-lattice relaxation time of a methylene group and a methinegroup is shorter than that of a methyl group, and accordingly, underthese measurement conditions, recovery of magnetization of all carbon isat least 99%. Integration for at least 20 hours was carried out for themeasurement.

(1-2) Content (P) of Propylene in Propylene-Butene Copolymer

The propylene content (P) in a propylene-butene copolymer was measuredby a ¹³C-NMR spectrum measuring method by means of an NMR apparatus(manufactured by JEOL Ltd., 400 MHz). A sample of from 350 to 500 mg,was completely dissolved by using about 2.2 ml of o-dichlorobenzene inan NMR sample tube of 10 mm in diameter. Then, as a lock solvent, about0.2 ml of deuterated benzene was added and homogenized, and then,measurement was carried out by a proton complete decoupling method at130° C. The measurement conditions were such that the pulse angle was90°, a pulse interval-pulse interval was 10 seconds, and the number ofintegration times was 6,000 times. The chemical shifts and contents ofpropylene and butene were calculated with reference to the descriptionby J. C. Randall, Macromolecules, 11, 592 (1978).

(2) Molecular Weight

Firstly, 20 mg of a sample was put into a 30 ml vial container, and 20 gof o-dichlorobenzene containing 0.04 wt % of BHT as a stabilizer wasadded. Using an oil bath heated to 135° C., the sample was dissolved andthen thermal filtration was carried out by a PTFE(polytetrafluoroethylene) filter having a pore diameter of 3 μm toprepare a sample solution having a polymer concentration of 0.1 wt %.Then, using GPC150CV manufactured by Waters and equipped with TSKgel GMH-HT (30 cm×4 columns) as columns and an R1 detector, GPC measurementwas carried out. The measurement conditions were such that injectionamount of the sample solution:

500 μl, the column temperature: 135° C., solvent: o-dichlorobenzene, andthe flow rate: 1.0 ml/min.

At the time of calculation of a molecular weight, using commerciallyavailable monodisperse polystyrene as a standard sample, from theviscosity equation of the polystyrene standard sample and apolypropylene, a calibration curve relating to the retention time andthe molecular weight was prepared, and calculation of the molecularweight of the propylene polymer was carried out.

As the viscosity equation, [α]=K·Mα was used, and for the polystyrene,K=1.38E-4, and α=0.70 were used, and for the propylene copolymer,K=1.03E-4, and α=0.78 were used.

(3) Graft Ratio

200 mg of a polymer and 4,800 mg of chloroform were put into a 10 mlsample bottle and heated at 50° C. for 30 minutes to completely dissolvethe polymer. Into a liquid cell made of NaCl and having an optical pathlength of 0.5 mm, chloroform was put and used as a background. Then, thedissolved polymer solution was put into the liquid cell, and usingFT-IR460plus, manufactured by JASCO Corporation, the infrared absorptionspectrum was measured by 32 integration times. The graft ratio of maleicanhydride was calculated by using a calibration curve prepared bymeasuring a solution having maleic anhydride dissolved in chloroform.And, based on a calibration curve separately prepared from the area ofthe absorption peak of a carbonyl group (the maximum peak in thevicinity of 1,780 cm⁻¹, 1,750-1,813 cm⁻¹), the content of the acidcomponent in the polymer was calculated, and it was taken as the graftratio (wt %).

(4) Dispersed Particle Size

It was measured by means of Microtrac UPA manufactured by Nikkiso Co.,Ltd. (model 9340, batch type, dynamic light scattering method/laserDoppler method). On such basis that the density of the dispersion was0.9 g/cm³, the particle shape was spherical, the refractive index ofparticles was 1.50, the dispersing medium was water, the refractiveindex of the dispersing medium was 1.33, the measurement was carried outfor a measurement time of 120 seconds or 180 seconds, and the 50%particle diameter (volume average particle diameter) and the 90%particle diameter were obtained by summation from the finest particlesize calculated by volume.

(5) Storage Stability

After adjusting the concentration of a resin dispersion so that thesolid content became 20 wt %, it was put into a sealed container havinga capacity of 50 ml and stored for three months in a constanttemperature chamber at 40° C., and the dispersed particle diameter afterthe storage was measured. One wherein there was no substantial change inthe dispersed particle diameter as between before and after the storagewas identified by ◯, and one wherein the dispersed particle diameterincreased (one agglomerated) was identified by X.

(6) Foaming Property

10 g of a sample was put into a 30 ml sample bottle and vigorouslystirred for one minute by a paint shaker. The sample bottle was left tostand still, and three minutes later, the foaming state was visuallyobserved.

◯: Foaming is not observed or slight.

x: Vigorous foaming is observed.

(7) Adhesion-100

A polypropylene of automobile exterior grade was injection-molded toobtain a substrate of 70 mm×150 mm×3 mm, and the substrate surface wascleaned with isopropyl alcohol. A resin dispersion having theconcentration adjusted so that the solid content became 20 wt % wassprayed thereon so that the applied amount would be about 5 to 10 g/m².Then, a test specimen after the coating was dried for 10 minutes at 80°C. in Safeven drier and then left to stand still at 25° C. for one hour.Then, on the coated film, as a base coat an acryl-polyol urethanecoating material Retane PG80III (manufactured by Kansai Paint Co., Ltd.)having a prescribed curing agent incorporated and further having theviscosity adjusted with a dedicated thinner, was sprayed so that thedried coated amount would be from 50 to 60 g/m² and baked at 80° C. for30 minutes to obtain a coated plate.

After the plate was left to stand at 25° C. for 24 hours, a testspecimen cross-cut in accordance with the cross-cut adhesion test methoddisclosed in JIS K 5400, was prepared and, after bonding an adhesivetape (product of Nichiban Co., Ltd.), peeled in a 90° direction, wherebythe adhesion was evaluated by the number of cross-cut sections notpeeled among 100 cross-cut sections.

(8) Adhesion-25

A propylene of automobile interior grade was injection-molded to obtaina substrate (test specimen) of 70 mm×150 mm×3 mm, and the substratesurface was cleaned with isopropyl alcohol. A sample was sprayed thereonso that the dry weight after coating would be about 15 g/m². Then, thetest specimen after the coating was baked at 70° C. for 20 minutes inSafeven drier to obtain a coated plate.

After the coated plate was left to stand at 23° C. for 24 hours, a testspecimen cross-cut with spacing of 2 mm to have 25 sections (5×5) wasprepared in accordance with the cross-cut adhesion test method disclosedin JIS K 5400 and, after bonding an adhesive tape (product of NichibanCo., Ltd.), peeled in a 90° direction, whereby the adhesion wasevaluated by the number of cross-cut sections not peeled among the 25cross-cut sections.

(9) Bleeding Out

A coated plate prepared in the same manner as in the adhesion-25 test,was left to stand for three days at 40° C., whereupon the exteriorappearance of the coated plate was visually evaluated and touched with afinger to judge the presence or absence of bleeding out of thesurfactant on the coated surface and its state in accordance with thefollowing standards.

◯: No bleeding out of the surfactant

Δ: Slight bleeding out of the surfactant

x: Bleeding out of the surfactant is distinctly observed, and stickinessis felt when touched with a finger.

(10) Water Resistance

A coated plate prepared in the same manner as in the adhesion-100 test,was immersed in warm water of 40° C. for 10 days, whereupon the exteriorappearance of the coating was visually evaluated. Further, its cross-cutadhesive test was carried out, and the adhesion was evaluated by thenumber of cross-cut sections not peeled among 100 cross-cut sections.

(11) GH Resistance

A coated plate prepared in the same manner as in the adhesion-100 testwas immersed in a mixed liquid of regular gasoline and ethanolmaintained at 20° C. (volume ratio: regular gasoline/ethanol=9/1),whereby the time until the peeling became 5 mm, was measured.

(12) Moisture Resistance

A coated plate prepared in the same manner as in the adhesion-25 test,was left to stand in a state of a relative humidity of 95% for one week,whereupon the exterior appearance of the coating was visually evaluated.Further, in the same manner as in the case of the adhesion-25 test, itscross-cut adhesion test was carried out, and the adhesion was evaluatedby the number of cross-cut sections not peeled among the 25 cross-cutsections.

(13) Beef Tallow Resistance

On a coated plate prepared in the same manner as in the adhesion-25test, beef tallow (reagent grade, manufactured by Wako Pure ChemicalIndustries, Ltd.) was applied so that the coated amount would be about 2g/100 cm² and left to stand at 80° C. for one day. The beef tallowcoated on the surface was cleaned with a neutral cleaner, whereupon theexterior appearance of the coating film was visually evaluated.

◯: Good

x: Swelling or rapture of the coating film observed.

Substances Used

Jeffamine M-1000: Methoxypoly(oxyethylene/oxypropylene)-2-propylamine(polyetheramine manufactured by Huntsman Corporation, molecular weight:1,000 (nominal value))

MD-1200: Vylonal MD-1200, manufactured by Toyobo

Co., Ltd (aqueous polyester resin dispersion, solid contentconcentration: 35%, resin Tg: 67° C., average particle diameter: 0.08μm)

BD-2250: Vondic 2250, manufactured by Dainippon Ink and Chemicals,Incorporated (aqueous polyurethane resin dispersion, resin solidcontent: 35%, average particle diameter: 0.105 μm)

ES-20: Rikabond ES-20, manufactured by CSC Co., Ltd (aqueous acrylicresin dispersion, solid content concentration: 440, resin Tg: 47° C.,average particle diameter: 0.10 μm)

EH-801: Hardlen EH-801 manufactured by Toyo Kasei

Kogyo Co., Ltd. (aqueous chlorinated propylene polymer resin dispersion,solid content concentration: 30%, average particle diameter: 0.036 μm,amount of surfactant: 30 wt %)

Thickener 636 (thickener): SN thickener 636, manufactured by San NopcoLimited

Examples of First Embodiment Preparation Example 1-1 Preparation ofPolypropylene

Into a 1,000 ml round bottomed flask, 110 ml of deionized water, 22.2 gof magnesium sulfate hepta hydrate and 18.2 g of sulfuric acid were putand dissolved with stirring. In this solution, 16.7 g of commercialavailable granulated montmorillonite (Benclay SL, manufactured byMizusawa Industrial Chemicals, Ltd.) was dispersed, then the temperaturewas raised to 100° C. over two hours, and stirring was carried out at100° C. for two hours. Then, the mixture was cooled to room temperatureover one hour, and the obtained slurry was subjected to filtration, anda wet cake was recovered. The recovered cake was again slurried with 500ml of deionized water in a 1,000 ml round bottomed flask and subjectedto filtration. This operation was repeated twice. The finally obtainedcake was dried overnight at 110° C. in a nitrogen atmosphere to obtain13.3 g of chemically treated montmorillonite.

To 4.4 g of the obtained chemically treated montmorillonite, 20 ml of atoluene solution of triethyl aluminum (0.4 mmol/ml) was added, followedby stirring at room temperature for one hour. To this suspension, 80 mlof toluene was added, and after stirring, the supernatant was removed.This operation was repeated twice, and then toluene was added to obtaina clay slurry (slurry concentration=99 mg clay/ml).

In a separate flask, 0.2 mmol of triisobutyl aluinum (manufactured byTosoh Akzo Corporation) was put, and 19 ml of the clay slurry obtainedand a toluene-diluted solution of 131 mg (57 μmol) ofdichloro[dimethylsilylene(cyclopentadienyl)(2,4-dimethyl-4H-1-azulenyl)hafniumwere added, followed by stirring at room temperature for 10 minutes toobtain a catalyst slurry (see JP-A-2004-002310 with respect to themethod for producing the catalyst, etc.).

Then, into an induction stirring type autoclave having an internalcapacity of 24 L, 11 L of toluene, 3.5 mmol of triisobutyl aluminum and2.64 L of liquid propylene were introduced. At room temperature, theabove catalyst slurry was introduced in its entire amount, then thetemperature was raised to 67° C., and while the total pressure duringthe polymerization was maintained to be constant at 0.65 MPa, stirringwas continued at the same temperature for two hours. After completion ofthe stirring, unreacted propylene was purged to terminate thepolymerization. The autoclave was opened, the toluene solution of thepolymer was recovered in its entire amount, and the solvent and clayresidue were removed to obtain 11 kg of a 13.5 wt % propylene polymertoluene solution (1.5 kg of propylene polymer). The weight averagemolecular weight of the obtained polypropylene was 191,000, and thestereoregularity (mmmm) was 45.8%.

Preparation Example 1-2 Preparation of Maleic Anhydride-ModifiedPolypropylene

Into a glass flask equipped with a reflux condenser, a thermometer and astirrer, 650 g of toluene and 350 g of the polypropylene obtained inPreparation Example 1-1 were put, and the interior was substituted withnitrogen gas, and the temperature was raised to 110° C. After raisingthe temperature, 14 g of maleic anhydride was added, and 4.7 g oft-butylperoxyisopropyl monocarbonate (Perbutyl I, manufactured by NOFCorporation) was added, whereupon stirring was continued at the sametemperature for 10 hours to carry out the reaction. After completion ofthe reaction, the system was cooled to near room temperature, andacetone was added, whereupon the precipitated polymer was collected byfiltration. Further, precipitation with acetone and filtration wererepeated, and the finally obtained polymer was washed with acetone. Thepolymer obtained after the washing was dried under reduced pressure toobtain a white powdery modified polymer. This modified polymer wassubjected to an infrared absorption spectrum measurement, whereby thecontent (graft ratio) of maleic anhydride groups was 1.25 wt % (0.125mmol/g as maleic anhydride groups, and 0.25 mmol/g as reactive groups).Further, the weight average molecular weight was 120,000.

Preparation Example 1-3 Preparation of Maleic Anhydride-ModifiedPolypropylene

The preparation was carried out in the same manner as in PreparationExample 1-2 except that the amount of maleic anhydride was changed to 28g, and the amount of t-butylperoxyisopropyl monocarbonate was changed to9.3 g. The content (graft ratio) of maleic anhydride groups was 2.4 wt %(0.24 mmol/g as maleic anhydride groups, and 0.48 mmol/g as reactivegroups). Further, the weight average molecular weight was 100,000.

Preparation Example 1-4 Preparation of Maleic Anhydride-ModifiedPolypropylene

The preparation was carried out in the same manner as in PreparationExample 1-2 except that the amount of maleic anhydride was changed to 21g, and the amount of t-butylperoxyisopropyl monocarbonate was changed to7.0 g. The content (graft ratio) of maleic anhydride groups was 1.6 wt %(0.16 mmol/g as maleic anhydride groups, and 0.32 mmol/g as reactivegroups). Further, the weight average molecular weight was 110,000.

Preparation Example 1-5 Preparation of Pigment-Dispersed Paste

A water-soluble acrylic resin (Joncryl 683 manufactured by JohnsonPolymer Corporation (resin acid value: 160 mgKOH/g)) was neutralizedwith 2-amino-2-methylpropanol and dissolved in water.

20 g of this aqueous solution (solid content concentration: 25 wt %),7.5 g of carbon black (manufactured by Mitsubishi Chemical Corporation),60 g of titanium oxide (R-5N, manufactured by Sakai Chemical IndustryCo., Ltd.), 2.5 g of a defoaming agent (SURFYNOL 440, manufactured byAir Products), 60 g of deionized water and 150 g of zirconia beads weremixed, and stirred and dispersed by a paint shaker for 30 minutes. Thedispersion was subjected to filtration with a metal net of 400 mesh toobtain a pigment-dispersed paste having a solid content concentration of50 wt %.

Preparation Example 1-6 Preparation of Maleic Anhydride-ModifiedPolypropylene Solution

A polypropylene was prepared in the same manner as Preparation Example1-1 except that the temperature during the polymerization was 71° C. andintroduction was carried out so that the hydrogen concentration in thesystem became 8,600 ppm, whereby 11.3 kg of a toluene solutioncontaining 15.5 wt % of the propylene polymer (corresponding to 1.75 kgof the propylene polymer) was obtained. The weight average molecularweight of the obtained polypropylene was 38,000, and thestereoregularity (mmmm) was 38.9%.

Into a glass flask equipped with a reflux condenser, a thermometer and astirrer, 300 g of the obtained polypropylene and 200 g of toluene wereput, and the interior of the container was substituted with nitrogengas, and the temperature was raised to 110° C. After raising thetemperature, 9.0 g of maleic anhydride was added, and 4.5 g oft-butylperoxyisopropyl monocarbonate (Perbutyl I, manufactured by NOFCorporation) was added, whereupon stirring was continued at the sametemperature for 7 hours to carry out the reaction. After completion ofthe reaction, 250 g of toluene was added to dilute the reaction solutionto a solid content concentration of 40 wt %, and the liquid temperaturewas adjusted to 60° C.

1,200 g of warm water of 60° C. was added thereto, followed by vigorousstirring for 30 minutes, whereupon the mixture was left to stand stillto separate it into a toluene layer and a water layer. The water layerwas removed, and unreacted maleic anhydride and by-products derived frommaleic anhydride were removed (warm water washing). This warm waterwashing was further repeated three times, and then, the obtained toluenelayer was heated for dehydration to obtain a toluene solution of maleicanhydride-modified polypropylene (solid content concentration: 40 wt %).

A part of this modified polymer was sampled, heated and dried, whereuponthe infrared absorption spectrum was measured. As a result, the content(graft ratio) of maleic anhydride groups was 1.2 wt % (0.12 mmol/g asmaleic anhydride groups, and 0.24 mmol/g as reactive groups), and theweight average molecular weight was 35,000.

Preparation Example 1-7 Preparation of Maleic Anhydride-ModifiedPropylene-Butene Copolymer

In a twin screw extruder with a diameter of 45 mm (PCM40, manufacturedby IKEGAI Ltd.), a blend comprising 10 kg of a propylene-butenecopolymer (TAFMER XM7070, Mitsui Chemicals, Inc.) (1 kg out of the 10 kgis one having pellets freeze-pulverized into a powder), 0.2 kg of maleicanhydride and 0.1 kg of Perbutyl I (manufactured by NOF Corporation),was melt-kneaded under the following extrusion conditions.

-   -   Cylinder temperature: 200° C.    -   Screw rotational speed: 200 rpm    -   Extrusion amount: 10 kg/hour

As a result of an infrared absorption spectrum measurement of theobtained modified polymer, the content (graft ratio) of maleic anhydridegroups was 0.6 wt % (as maleic anhydride groups: 0.06 mmol/g, asreactive groups:

0.12 mmol/g), and the weight average molecular weight was 78,000.

Example 1-1

Into a glass flask equipped with a reflux condenser, a thermometer and astirrer, 30 g of the maleic anhydride-modified polypropylene prepared inPreparation Example 1-2 (content of maleic anhydride groups: 3.75 mmol)and 60 g of toluene were added and completely dissolved by raising thetemperature to 110° C. Then, a solution having 7.5 g of Jeffamine M-1000(7.5 mmol, corresponding to 25 parts by weight of the hydrophilicpolymer (B) per 100 parts by weight of the polyolefin (A)) dissolved in10 g of toluene, was added and reacted at 110° C. for 3 hours.

After cooling, toluene was distilled off under reduced pressure toobtain 37 g of a yellow polymer. The obtained product was subjected toan infrared absorption spectrum analysis, and as a result, it wasobserved that a peak corresponding to maleic anhydride in the vicinityof 1,784 cm⁻¹ was extinct, and the maleic anhydride-modifiedpolypropylene and the polyether amine were completely bonded. It is inthe form of a graft copolymer having the polyether amine graft-bonded tothe maleic anhydride-modified polypropylene.

To 25 g of the obtained yellow polymer, 75 g of THF was added, and thepolymer was completely dissolved at 60° C. At the same temperature, 84 gof pure water was dropwise added thereto over a period of one hour, toobtain a hazy yellow solution. This solution was cooled to 40° C., andby lowering the reduced pressure degree gradually from a reducedpressure degree of 0.03 MPa to 0.0045 MPa, distillation under reducedpressure was carried out until the concentration became 25 wt %, toobtain a translucent slightly yellow resin dispersion. It is consideredthat the dispersed particle sizes are so fine that the dispersion lookstranslucent.

The dispersed particle sizes were measured, whereby the 50% particlediameter was 0.068 μm. The adhesion, water resistance and GH resistancewere evaluated. The results are shown in Table 1-1.

The methoxypoly(oxyethylene/oxypropylene)-2-propylamine (JeffamineM-1000) used in Example 1-1 had an insoluble content of at most 1 wt %,when dissolved at a concentration of 10 wt % in water of 25° C., and itis a hydrophilic polymer.

Example 1-2

44 g of a yellow polymer was obtained in the same manner as in Example1-1 except that 30 g of the maleic anhydride-modified polypropyleneobtained in Preparation Example 1-3 (content of maleic anhydride groups:7.2 mmol) was used as the maleic anhydride-modified polypropylene, and14.4 g of Jeffamine M-1000 (14.4 mmol, corresponding to 48 parts byweight of the hydrophilic polymer (B) per 100 parts by weight of thepolyolefin (A)) was used. It is in the form of a graft copolymer havingthe polyether amine graft-bonded to the maleic anhydride-modifiedpolypropylene.

To 20 g of the obtained yellow polymer, 80 g of THF was added, and thepolymer was completely dissolved at 60° C. At the same temperature, 100g of pure water was dropwise added thereto over a period of one hour, toobtain a yellow solution. This solution was cooled to 40° C., and bylowering the reduced pressure degree gradually from a reduced pressuredegree of 0.03 MPa to 0.0045 MPa, distillation under reduced pressurewas carried out until the concentration became 20 wt %, to obtain atransparent yellow resin dispersion. It is considered that the dispersedparticle sizes are so fine that the dispersion looks almost transparent.

The dispersed particle sizes were measured, whereby the 50% particlediameter was 0.011 μm. In the same manner as in Example 1-1, theadhesion, water resistance and GH resistance were evaluated. The resultsare shown in Table 1-1.

Example 1-3

Into a glass flask equipped with a reflux condenser, a thermometer and astirrer, 30 g of the maleic anhydride-modified polypropylene prepared inPreparation Example 1-4 (content of maleic anhydride groups: 4.8 mmol)and 70 g of toluene were added and completely dissolved by raising thetemperature to 110° C. Then, a solution having 4.5 g of Jeffamine M-1000(4.5 mmol, corresponding to 15 parts by weight of the hydrophilicpolymer (B) per 100 parts by weight of the polyolefin (A)) dissolved in4.5 g of toluene, was added and reacted at 110° C. for one hour. Then,0.4 g (4.5 mmol) of morpholine was added and reacted at 110° C. for onehour.

After cooling, toluene was distilled off under reduced pressure toobtain 34 g of the yellow polymer. The obtained product was subjected toan infrared absorption spectrum analysis, and as a result, it wasobserved that 90% of a peak corresponding to maleic anhydride in thevicinity of 1,784 cm⁻¹ was extinct, and the maleic anhydride-modifiedpolypropylene and the polyether amine were bonded. It is in the form ofa graft copolymer having the polyether amine graft-bonded to the maleicanhydride-modified polypropylene.

To 25 g of the obtained yellow polymer, 75 g of THF was added, and thepolymer was completely dissolved at 60° C. At the same temperature, 84 gof pure water was dropwise added thereto over a period of one hour, toobtain a hazy yellow solution. This solution was cooled to 40° C., andby lowering the reduced pressure degree gradually from a reducedpressure degree of 0.03 MPa to 0.0045 MPa, distillation under reducedpressure was carried out until the concentration became 25 wt %, toobtain a translucent slightly yellow resin dispersion. It is consideredthat the dispersed particle sizes are so fine that the dispersion lookstranslucent.

The dispersed particle sizes were measured, whereby the 50% particlediameter was 0.086 μm. The adhesion, water resistance and GH resistancewere evaluated. The results are shown in Table 1-1.

Reference Example

39 g of a yellow polymer was obtained in the same manner as in Example1-1 except that instead of the maleic anhydride-modified polypropylene,a maleic anhydride-modified chlorinated polypropylene (manufactured byToyo Kasei Kogyo Co., Ltd., the content (graft ratio) of maleicanhydride groups was 2.1 wt % (0.21 mmol/g)) was used, 9 g of JeffamineM-1000 (9 mmol, corresponding to 30 parts by weight of the hydrophilicpolymer (B) per 100 parts by weight of the polyolefin (A)) was used, andthe polymer was dissolved in 9 g of toluene. It is in the form of agraft copolymer having the polyether amine graft-bonded to the maleicanhydride-modified chlorinated polypropylene.

To 25 g of the obtained yellow polymer, 75 g of THF was added, and thepolymer was completely dissolved at 60° C. At the same temperature, 100g of pure water was dropwise added thereto over a period of one hour, toobtain a yellow solution. This solution was cooled to 40° C., and bylowering the reduced pressure degree gradually from a reduced pressuredegree of 0.03 MPa to 0.0045 MPa, distillation under reduced pressurewas carried out until the concentration became 20 wt %, to obtain atransparent yellow resin dispersion. It is considered that the dispersedparticle sizes are so fine that the dispersion looks almost transparent.

The dispersed particle sizes were measured, whereby the 50% particlediameter was 0.098 μm. In the same manner as in Example 1-1, theadhesion, water resistance and GH resistance were evaluated. The resultsare shown in Table 1-1.

Comparative Example 1-1

Into a glass flask equipped with a reflux condenser, a thermometer and astirrer, 20 g of the maleic anhydride-modified polypropylene obtained inPreparation Example 1-2 and 80 g of toluene were put and completelydissolved by raising the temperature to 110° C. After cooling to 50° C.,3 g of polyoxyethylene cetyl ether (nonionic surfactant, EMULGEN 220,manufactured by Kao Corporation, HLB=14.2) and 3 g of polyoxyethylenelauryl ether (nonionic surfactant, EMULGEN 147, manufactured by KaoCorporation, HLB=16.3) were added and dissolved, followed by cooling to35° C.

140 g of water was gradually added thereto and thoroughly stirred, andthen using an internal shearing type emulsifier Clearmix CLM-0.8S(manufactured by M Technique Co., Ltd.), emulsifying was carried out at21,000 rpm for 3 minutes. Then, into the system, an aqueous solutionhaving 2-amino-2-methyl-1-propanol diluted with water to 10 wt %, wasadded, and the pH was adjusted to 8. This crude emulsified product wassubjected to distillation of toluene by gradually reducing the reducedpressure degree from a reduced pressure degree of 0.02 MPa to 0.0045MPa, to obtain a milky white resin dispersion having a concentration of25 Wt %.

The dispersed particle sizes were measured, whereby the 50% particlediameter was 0.25 μm. In the same manner as in Example 1-1, theadhesion, water resistance and GH resistance were evaluated. The resultsare shown in Table 1-1. Both the 50% particle diameter and the 90%particle diameter were substantially larger than Examples, andagglomeration was observed by storage for three months, and the waterresistance was poor.

Comparative Example 1-2

37 g of a yellow polymer was obtained in the same manner as in Example1-1 except that to 30 g of the maleic anhydride-modified polypropyleneobtained in Preparation 1-2 (content of maleic anhydride groups: 3.75mmol), 7.5 g of the polyester polyol (P-2010, manufactured by KurarayCo., Ltd., molecular weight: 2,000 (nominal value)) (3.75 mmol,corresponding to 25 parts by weight per 100 parts by weight of thepolyolefin (A)) and 0.3 g of dimethylbenzylamine were added. It is inthe form of a graft copolymer having the polyester polyol graft-bondedto the maleic anhydride-modified polypropylene.

To 20 g of the obtained yellow polymer, 80 g of THF was added, and thepolymer was completely dissolved at 60° C. At the same temperature, 100g of pure water was dropwise added thereto over a period of one hour,whereby the yellow polymer was separated, and no resin dispersion wasobtained.

The polyester polyol used in Comparative Example 1-2 (P-2010,manufactured by Kuraray Co., Ltd.,) is not a hydrophilic polymer, as theinsoluble content exceeds 1 wt % when it is dissolved in water at 25° C.to a concentration of 10 wt %.

TABLE 1-1 Dispersed particle sizes immediately Dispersed particle afterpreparation sizes after 3 months Graft 50% 90% 50% 90% Maleic-modifiedratio Particle Particle Particle Particle Storage Adhesion- Water GHpolyolefin (wt %) diameter diameter diameter diameter stability 100resistance resistance Ex. 1-1 Prep. Ex. 1-2 1.25 0.068 0.12 0.071 0.12 ◯100/100 100/100 >60 min Ex. 1-2 Prep. Ex. 1-3 2.4 0.011 0.015 0.0110.015 ◯ 100/100 100/100 >60 min Ex. 1-3 Prep. Ex. 1-4 1.6 0.086 0.170.090 0.19 ◯ 100/100 100/100 >60 min Ref. Ex. Chlorinated PP 2.1 0.0980.18 0.096 0.19 ◯ 100/100 100/100 >60 min Comp. Ex. 1-1 Prep. Ex. 1-21.25 0.25 3.1 0.28 6.0 X 100/100  80/100 >60 min Comp. Ex. 1-2 Prep. Ex.1-2 1.25 No resin dispersion obtained Comp. Ex. 1-4 Prep. Ex. 1-4 1.6 Noresin dispersion obtained

Example 1-5 to 1-8, and Comparative Example 1-3

To 10 g of each of the resin dispersions (solid content concentration:25 wt %) of Examples 1-1 to 1-4 and Comparative Example 1-1, 10 g of thepigment-dispersed paste (solid content concentration: 50 wt %) ofPreparation Example 1-5 and 5.7 g of the aqueous acryl resin dispersionES-20 were mixed to obtain a coating material, and in the same manner asin Example 1-1, the adhesion, water resistance, GH resistance andbleeding out were evaluated. The results are shown in Table 1-2.

TABLE 1-2 Maleic-modified Graft ratio Water GH polyolefin (wt %)Adhesion-100 resistance resistance Bleeding out Ex. 1-5 Prep. Ex. 1-21.25 100/100 100/100 >60 min ◯ Ex. 1-6 Prep. Ex. 1-3 2.4 100/100100/100 >60 min ◯ Ex. 1-7 Prep. Ex. 1-4 1.6 100/100 100/100 >60 min ◯Ex. 1-8 Chlorinated PP 2.1 100/100 100/100 >60 min ◯ Comp. Ex. 1-3 Prep.Ex. 1-2 1.25  24/100  16/100 >60 min X

Example 1-9

Into a glass flask equipped with a reflux condenser, a thermometer and astirrer, 650 g of toluene and 350 g of a propylene-butene copolymer(Tafiner XM-7070, manufactured by Mitsui Chemicals, Inc.) were put, andthe interior of the container was replaced with nitrogen gas, and thetemperature was raised to 110° C. After raising the temperature, 35 g ofmaleic anhydride was added, and 10.7 g of t-butylperoxyisopropylmonocarbonate (Perbutyl I, manufactured by NOF Corporation) was added,whereupon stirring was continued at the same temperature for 10 hours tocarry out the reaction. After completion of the reaction, the system wascooled to near room temperature, acetone was added, and a precipitatedpolymer was collected by filtration. Further, precipitation with acetoneand filtration were repeated, and the finally obtained polymer waswashed with acetone. The polymer obtained after the washing was driedunder reduced pressure to obtain a white powdery maleicanhydride-modified polymer. The infrared absorption spectrum measurementof this modified polymer was carried out, whereby the content (graftratio) of the maleic anhydride groups was 2.1 wt % (0.21 mmol/g asmaleic anhydride groups, and 0.42 mmol/g as carboxy acid groups).Further, the weight average molecular weight was 110,000.

Then, into a glass flask equipped with a reflux condenser, a thermometerand a stirrer, 30 g of the obtained maleic anhydride-modified polymer(content of maleic anhydride groups: 6.3 mmol) and 70 g of toluene wereadded and completely dissolved by raising the temperature to 110° C.Then, a solution having 6 g of Jeffamine M-1000 (6 mmol, correspondingto 20 parts by weight of the hydrophilic polymer (B) per 100 parts byweight of the copolymer (A)) dissolved in 6 g of toluene, was added andreacted at 110° C. for one hour. Then, 0.53 g (6 mmol) of morpholine wasadded and reacted at 110° C. for one hour.

A small amount was sampled from the reaction solution, and toluene wasdistilled off under reduced pressure, and then an infrared absorptionspectrum analysis was carried out, whereby it was observed that 90% of apeak corresponding to maleic anhydride in the vicinity of 1,784 cm⁻¹ wasextinct, and the maleic anhydride-modified polymer and the polyetheramine were bonded. It is in the form of a graft copolymer having thepolyether amine graft-bonded to the maleic anhydride-modified polymer.

While the temperature of the obtained reaction solution was maintainedat 60° C., a mixed liquid of 120 g of isopropanol and 30 g of water wasdropwise added over one hour under heating with stirring to obtain ahazy slightly yellow liquid. Further, a mixed liquid of 30 g ofisopropanol and water was dropwise added over one hour while thetemperature of the reaction solution was maintained at 60° C., to obtaina translucent yellow solution. This solution was cooled to 45° C., andby lowering the reduced pressure degree gradually from a reducedpressure degree of 0.02 MPa to 0.004 MPa, toluene, isopropanol and waterwere distilled off under reduced pressure until the polymerconcentration became 25 wt %, to obtain a slightly yellow transparentaqueous resin dispersion. It is considered that the dispersed particlesizes are so fine that the dispersion looks transparent.

The dispersed particle sizes were measured, whereby the 50% particlediameter was 0.099 μm, and the 90% particle diameter was 0.184 μm. Theevaluation results of the adhesion of the obtained aqueous resindispersion are shown in Table 1-3. Also, the propylene content in thepropylene-butene copolymer used (Tafiner XM-7070, manufactured by MitsuiChemicals, Inc.) is shown.

Here, evaluation of the adhesion in this Example was carried out asfollows.

A polypropylene of automobile exterior grade was injection-molded toobtain a substrate (test specimen) of 70 mm×150 mm×3 mm, and thesubstrate surface was cleaned with isopropyl alcohol. A test sample wassprayed thereon so that the coated amount (dry weight after coating)would be about 15 g/m². Then, a test specimen after the coating wasdried and baked at 80° C. for 40 minutes in Safeven drier to obtain acoated plate.

After the coated plate was left to stand at 23° C. for 24 hours, a testspecimen cross-cut with spacing of 2 mm to have 25 sections (5×5) wasprepared in accordance with the cross-cut adhesion test method disclosedin JIS K 5400, and after bonding an adhesive tape (product of NichibanCo., Ltd.), peeled in a 90° direction, whereby the adhesion wasevaluated by the number of cross-cut sections not peeled among the 25cross-cut sections.

TABLE 1-3 Content of Dispersed particle sizes propylene Graftimmediately after preparation (P) ratio 50% Particle 90% ParticleAdhesion- (mol %) (wt %) diameter diameter 25 Ex. 1-9 73.9 2.1 0.0990.184 25/25

Comparative Example 1-4

Into a glass flask equipped with a reflux condenser, a thermometer and astirrer, 30 g of the maleic anhydride-modified polypropylene obtained inPreparation Example 1-4 (content of maleic anhydride groups: 4.8 mmol)and 70 g of toluene were put and completely dissolved by raising thetemperature to 110° C. Then, 2 g (23 mmol) of morpholine was added andreacted at 110° C. for one hour. After cooling, toluene was distilledoff under reduced pressure to obtain 32 g of a yellow polymer.

To 25 g of the obtained yellow polymer, 75 g of THF was added, and thepolymer was completely dissolved at 60° C. At the same temperature, 84 gof pure water was dropwise added over one hour, whereby the yellowpolymer was separated, and no resin dispersion was obtained.

Here, morpholine is a hydrophilic compound but not a hydrophilic polymeras its molecular weight is 89.

Comparative Example 1-5 Dispersing of Non-Modified Polypropylene byMeans of Surfactant

A resin dispersion was obtained in the same manner as in ComparativeExample 1-1 except that the polypropylene obtained in PreparationExample 1-1 was used.

The dispersed particle sizes were measured, whereby the 50% particlediameter was 0.32 μm. Then, in the same manner as in Example 1-1,evaluation of the adhesion was carried out, whereby at all cross-cutsections, the coated film was peeled from the base coating, and theresult was 0/100.

Comparative Example 1-6 Dispersing of Non-Modified Polypropylene byMeans of Jeffamine M-1000

Into a glass flask equipped with a reflux condenser, a thermometer and astirrer, 25 g of the polypropylene obtained in Preparation Example 1-1and 70 g of THF were added and completely dissolved by raising thetemperature to 60° C. A solution having 9 g (9 mmol) of Jeffamine M-1000dissolved in 27 g of THF, was added thereto, and then the temperaturewas adjusted to 60° C. Then, at the same temperature, 84 g of pure waterwas dropwise added over one hour, whereby during the dropwise addition,the liquid turbidified, the resin was separated, and no resin dispersionwas obtained.

Namely, Jeffamine M-1000 has no ability to disperse the non-modifiedpolypropylene and is not a surfactant.

Example 1-10

Into a glass flask equipped with a reflux condenser, a thermometer and astirrer, 600 g of the toluene solution of the maleic anhydride-modifiedpolypropylene obtained in Preparation Example 1-6 (content of maleicanhydride-modified polypropylene: 240 g) was added by raising thetemperature to 110° C. A solution having 36.0 g of Jeffamine M-1000(36.0 mmol, corresponding to 15 parts by weight per 100 parts by weightof the propylene polymer) dissolved in 54.0 g of toluene, was added andreacted at 110° C. for one hour.

After cooling, a part of the reaction solution was sampled, and thetoluene was distilled off under reduced pressure, whereupon the infraredabsorption spectrum analysis of the polymer obtained was carried out,whereby it was confirmed that a peak corresponding to maleic anhydridein the vicinity of 1,784 cm⁻¹ decreased, and the maleicanhydride-modified polypropylene and the polyether amine were bonded. Itis in the form of a graft copolymer having the polyether aminegraft-bonded to the maleic anhydride-modified polypropylene.

Then, 100 g of the obtained toluene solution of the polyalkyleneglycol-modified polypropylene (polymer content: 40 g) was added to aglass flask equipped with a reflux condenser, a thermometer and astirrer, and the temperature was raised to 65° C.

A mixed solvent comprising 120 g of isopropyl alcohol (IPA) and 30 g ofdistilled water was dropwise added thereto over one hour to obtain atranslucent slightly yellow solution. The pressure was gradually reducedand 120 g of the mixed solvent of toluene/IPA/water was distilled offunder reduced pressure.

Then, a mixed solvent of 15 g of IPA and 135 g of distilled water wasdropwise added at 65° C. over 30 minutes, and then the solvent wasdistilled off under reduced pressure in the same manner to obtain awhite resin dispersion having a solid content concentration of 25 wt %.

The particle sizes were measured, whereby the 50% particle diameter was0.142 μm. Further, upon expiration of three months, the particle sizeswere measured, and the storage stability was evaluated. The results areshown in Table 1-4.

Example 1-11

A slightly yellow translucent resin dispersion was obtained in the samemanner as in Example 1-10 except that the dropwise added mixed solventat the first stage was changed to a mixture comprising 120 g of IPA, 30g of distilled water and 0.4 g of 2-amino-2-methyl-1-propanol.

The dispersed particle sizes were measured, whereby the 50% particlediameter was 0.084 μm. The results are shown in Table 1-4.

Example 1-12

A slightly yellow translucent resin dispersion was obtained in the samemanner as in Example 1-10 except that the dropwise added mixed solventat the first stage was changed to a mixture comprising 120 g of IPA, 30g of distilled water and 0.4 g of N,N-dimethylethanolamine.

The dispersed particle sizes were measured, whereby the 50% particlediameter was 0.076 μm. The results are shown in Table 1-4.

Example 1-13

Into a glass flask equipped with a reflux condenser, a thermometer and astirrer, 100 g of the maleic anhydride-modified propylene-butenecopolymer prepared in Preparation Example 1-7 (content of maleicanhydride groups: 6 mmol) and 200 g of toluene were added, and thetemperature was raised to 65° C. Then, 12 g (12 mmol) of JeffamineM-1000 was added and reacted at the same temperature for one hour.

A mixed solvent comprising 120 g of IPA and 30 g of distilled water wasprepared, and to one fourth thereof, 1.1 g of2-methyl-2-amino-1-propanol was added to obtain a solution, which wasdropwise added over 30 minutes. Then, the remaining mixed solvent of IPAand distilled water was dropwise added at the same temperature for onehour, to obtain a translucent slightly yellow solution. The pressure wasgradually reduced and 120 g of the mixed solvent of toluene/IPA/waterwas distilled off under reduced pressure.

Then, a mixed solvent of 15 g of IPA and 135 g of distilled water wasdropwise added at 65° C. over 30 minutes, and then the solvent wasdistilled off under reduced pressure in the same manner to obtain awhite resin dispersion having a solid content concentration of 25 wt %.

The particle sizes were measured, whereby the 50% particle diameter was0.132 μm. The results are shown in Table 1-4.

TABLE 1-4 Dispersed particle sizes immediately Dispersed particle afterpreparation sizes after 3 months Maleic-modified Graft ratio 50%Particle 90% Particle 50% Particle 90% Particle Storage polyolefin (wt%) diameter diameter diameter diameter stability Ex. 1-10 Prep. Ex. 1-61.2 0.142 0.22 0.16 0.23 ◯ Ex. 1-11 Prep. Ex. 1-6 1.2 0.084 0.14 0.0900.15 ◯ Ex. 1-12 Prep. Ex. 1-6 1.2 0.076 0.14 0.085 0.15 ◯ Ex. 1-13 Prep.Ex. 1-7 0.6 0.132 0.24 0.14 0.25 ◯

Examples Relating to Second Embodiment Preparation Example 2-1Preparation of Polypropylene

In the same manner as in Preparation Example 1-1, a catalyst slurry wasobtained.

Then, into an induction stirring type autoclave having an internalcapacity of 24 L, 11 L of toluene, 3.5 mmol of triisobutyl aluminum and2.64 L of liquid propylene were introduced. At room temperature, theabove catalyst slurry was introduced in its entire amount, then thetemperature was raised to 63° C., and while the total pressure duringthe polymerization was maintained to be constant at 0.65 MPa, stirringwas continued at the same temperature for two hours. After completion ofthe stirring, unreacted propylene was is purged to terminate thepolymerization. The autoclave was opened, the toluene solution of thepolymer was recovered in its entire amount, and the solvent and clayresidue were removed to obtain 11 kg of a 12.8 wt % propylene polymertoluene solution (1.4 kg of propylene polymer). The weight averagemolecular weight of the obtained polypropylene was 180,000, and thestereoregularity (mmmm) was 47.5%.

Preparation Example 2-2 Preparation of Maleic Anhydride-ModifiedPolypropylene

Into a glass flask equipped with a reflux condenser, a thermometer and astirrer, 350 g of the polypropylene obtained in Preparation Example 2-1and 650 g of toluene were put, and the interior of the container wasreplaced with nitrogen gas, and the temperature was raised to 110° C.After raising the temperature, 17.5 g of maleic anhydride was added, and8.75 g of t-butylperoxyisopropyl monocarbonate (Perbutyl I, manufacturedby NOF Corporation) was added, whereupon stirring was continued at thesame temperature for 7 hours to carry out the reaction. After completionof the reaction, the system was cooled to near room temperature, andacetone was added, whereupon the precipitated polymer was collected byfiltration. Further, precipitation with acetone and filtration wererepeated, and the finally obtained polymer was washed with acetone. Thepolymer obtained after the washing was dried under reduced pressure toobtain a white powdery maleic anhydride-modified polymer. The infraredabsorption spectrum measurement of this modified polymer was carriedout, whereby the content (graft ratio) of maleic anhydride groups was1.2 wt % (0.12 mmol/g). Further, the weight average molecular weight was110,000.

Preparation Example 2-3 Preparation of Aqueous Resin Dispersion ofPolyalkylene Glycol-Modified Polypropylene

Into a glass flask equipped with a reflux condenser, a thermometer and astirrer, 30 g of the maleic anhydride-modified polypropylene prepared inPreparation Example 2-2 (content of maleic anhydride groups: 3.6 mmol)and 70 g of toluene were added and completely dissolved by raising thetemperature to 110° C. Then, a solution having 7.5 g of Jeffamine M-1000(7.5 mmol, corresponding to 25 parts by weight per 100 parts by weightof the propylene polymer) dissolved in 7.5 g of toluene, was added andreacted at 110° C. for 3 hours.

After cooling, toluene was distilled off under reduced pressure toobtain 37 g of the yellow polymer. The infrared absorption analysis ofthe obtained product was carried out, whereby it was confirmed that apeak corresponding to maleic anhydride in the vicinity of 1,784 cm⁻¹ wasextinct, and the maleic anhydride-modified polypropylene and thepolyether amine were completely bonded. It is in the form of a graftcopolymer having the polyether amine graft-bonded to the maleicanhydride-modified polypropylene.

To 20 g of the obtained yellow polymer, 80 g of THF was added, and thepolymer was completely dissolved at 65° C. At the same temperature, 100g of pure water was dropwise added thereto over a period of one hour, toobtain a hazy yellow solution. This solution was cooled to 40° C., andby lowering the reduced pressure degree gradually from a reducedpressure degree of 0.03 MPa to 0.0045 MPa, THF and water were distilledoff under reduced pressure until the concentration became 25 wt %, toobtain a translucent slightly yellow aqueous resin dispersion. It isconsidered that the dispersed particle sizes are so fine that thedispersion looks translucent.

The dispersed particle sizes were measured, whereby the 50% particlediameter was 0.04 μm, and the 90% particle diameter was 0.07 μm.

Here, Jeffamine M-1000 had an insoluble content of at most 1 wt % whenit was dissolved in water at 25° C. at a concentration of 10 wt %, andis a hydrophilic polymer.

Preparation Example 2-4: Preparation of Aqueous Dispersion of MaleicAcid-Modified Polypropylene

Into a glass flask equipped with a reflux condenser, a thermometer and astirrer, 20 g of the maleic anhydride-modified polypropylene obtained inPreparation Example 2-2 and 80 g of toluene were put and completelydissolved by raising the temperature to 110° C. After cooling to 50° C.,5 g of polyoxyethylene cetyl ether (nonionic surfactant, EMULGEN 220,manufactured by Kao Corporation, HLB=14.2) and 5 g of polyoxyethylenelauryl ether (nonionic surfactant, EMULGEN 147, manufactured by KaoCorporation, HLB=16.3) were added and dissolved, followed by cooling to35° C.

100 g of water was added thereto and thoroughly stirred, and then usingan internal shearing type emulsifier Clearmix CLM-0.8S (manufactured byM Technique Co., Ltd.), emulsifying was carried out at 21,000 rpm for 3minutes. Then, into the system, an aqueous solution having2-amino-2-methyl-1-propanol diluted with water to 10 wt %, was added,and the pH was adjusted to 8. From this crude emulsified product,toluene and water were distilled off by lowering the reduced pressuredegree gradually from a reduced pressure degree of 0.02 MPa to 0.0045MPa, to obtain a milky white resin dispersion having a concentration of25 wt %.

The dispersed particle sizes were measured, whereby the 50% particlediameter was 0.25 μm, and the 90% particle diameter was 3.1 μm. Both the50% particle diameter and the 90% particle diameter were substantiallylarger than Examples.

Preparation Example 2-5 Preparation of Pigment-Dispersed Paste

A water-soluble acrylic resin (Joncryl 683 manufactured by JohnsonPolymer Corporation (resin acid value: 160 mgKOH/g)) was neutralizedwith 2-amino-2-methylpropanol and dissolved in water.

20 g of this aqueous solution (solid content concentration: 25%), 7.5 gof carbon black (manufactured by Mitsubishi Chemical Corporation), 60 gof titanium oxide (R-5N, manufactured by Sakai Chemical Industry Co.,Ltd.), 2.5 g of a defoaming agent (SURFYNOL 440, manufactured by AirProducts), 60 g of deionized water and 150 g of zirconia beads weremixed, and stirred and dispersed by a paint shaker for 30 minutes. Thedispersion was subjected to filtration with a metal net of 400 mesh toobtain a pigment-dispersed paste having a solid content concentration of50 wt %.

Preparation Example 2-6 Preparation of Propylene Polymer

11 kg of a 12.9 wt % propylene-ethylene copolymer toluene solution wasobtained (1.42 kg of the propylene polymer) in the same manner as inPreparation Example 2-1 except that the polymerization temperature was50° C., the total pressure during the polymerization was 0.5 MPa, andethylene was introduced in an amount corresponding to 6.3% of the totalpressure. The weight average molecular weight of the obtainedpropylene-ethylene copolymer was 217,000, the stereoregularity (mmmm)was 40.1%, and the ethylene content was 3.1 mol %.

Preparation Example 2-7 Preparation of Maleic Anhydride-ModifiedPropylene Polymer

A maleic anhydride-modified propylene ethylene copolymer was obtained inthe same manner as in Preparation Example 2-2 except that thepropylene-ethylene copolymer obtained in Preparation Example 2-6 wasused. The infrared absorption spectrum measurement of this modifiedpolymer was carried out, whereby the content (graft ratio) of maleicanhydride groups was 1.3 wt % (0.12 mmol/g). Further, the weight averagemolecular weight was 116,000.

Preparation Example 2-8 Preparation of an Aqueous Dispersion ofPolyalkylene Glycol-Modified Propylene Polymer

A translucent slightly yellow aqueous resin dispersion was obtained inthe same manner as in Preparation Example 2-3 except that the maleicanhydride-modified propylene-ethylene copolymer of Preparation Example2-7 was used. It is considered that the dispersed particle sizes are sofine that the dispersion looks translucent.

The dispersed particle sizes were measured, whereby the 50% particlediameter was 0.016 μm, and the 90% particle diameter was 0.027 μm.

Example 2-1 Aqueous Resin Dispersion

As a propylene polymer resin, 12 g (3 g as solid content) of thepolyalkylene glycol-modified polypropylene aqueous resin dispersionobtained in Preparation Example 2-3 was used and blended with 20 g (7 gas solid content) of Vylonal MD-1200, to obtain an aqueous resindispersion of propylene polymer/polyester=30/70 (weight ratio). Theevaluation results are shown in Table 2-1.

Examples 2-2 and 2-3 Comparative Examples 2-1 to 2-6

Aqueous resin dispersions were prepared in the same manner as in Example2-1 except that the compositions as shown in Table 2-1 were employed.The evaluation results are shown in Table 2-1. In the Table, component(IC) and component (ID) represent values calculated as solid contents.

TABLE 2-1 50% Particle Ex. Ex. Ex. Comp. Ex. Comp. Ex. Comp. Ex. Comp.Ex. Comp. Ex. Comp. Ex. diameter 2-1 2-2 2-3 2-1 2-2 2-3 2-4 2-5 2-6Component Prep. Ex. 2-3 0.040 μm 3 5 3 (IC) Prep. Ex. 2-4  0.25 μm 3 5 3EH-801 0.036 μm 3 5 3 Component MD-1200 0.050 μm 7 7 7 (ID) BD-22500.105 μm 5 5 5 ES-20 0.100 μm 7 7 7 Thickener 636 0.1 0.1 0.1 0.1 0.10.1 Deionized water 2 3.3 2 IA content *1 25.5 44.4 25.5 30.0 50.0 30.030.0 50.0 30.0 (IC + ID) content *2 31.3 29.2 35.8 31.3 29.2 35.8 31.329.2 35.8 Amount of surfactant/ 0% 0% 0% 9% 15% 9% 9% 15% 9% (IC + ID)Particle diameter ratio 0.80 0.38 0.40 5.00 2.38 2.50 0.72 0.34 0.36(IC/ID) Foaming property ◯ ◯ ◯ X X X X X X Adhesion-25 25/25 25/25 25/250/25 25/25 0/25 0/25 25/25 5/25 Bleeding out ◯ ◯ ◯ Δ X Δ ◯ Δ ◯ Moistureresistance 22/25 25/25 24/25 0/25 23/25 0/25 0/25  0/25 5/25 *1 IAcontent = IA/(IA + ID)*100 *2 (IC + ID) content = (IC + ID)/(IC + ID +water)*100

The aqueous resin dispersions of Examples 2-1 to 2-3 are excellent ineach of the foaming property, initial adhesion and moisture resistance,and no bleeding out was observed, and thus they were found to beexcellent.

Examples 2-4 to 2-6 Comparative Examples 2-7 to 2-9 Coating Materials

The coating materials were prepared to have compositions as identifiedin Table 2-2. Here, butyl cellosolve (ethylene glycol monobutyl ether)was incorporated as a film-forming assistant. The evaluation results areshown in Table 2-2. In the Table, component (IC) and component (ID)represent values calculated as solid contents.

TABLE 2-2 50% Particle Ex. Ex. Ex. Comp. Ex. Comp. Ex. Comp. Ex.diameter 2-4 2-5 2-6 2-7 2-8 2-9 Component (IC) Prep. Ex. 2-3 0.040 μm 77 Prep. Ex. 2-4  0.25 μm 7 7 Prep. Ex. 2-8 0.016 μm 3 EH-801 0.036 μm 7Component (ID) ES-20 0.100 μm 3 7 3 3 MD-1200 0.050 μm 3 3 Component(IE) Prep. Ex. 2-5 20 20 20 20 20 20 Thickener 636 0.1 0.1 0.1 0.1 0.10.1 Butyl cellosolve 2 2 2 2 2 2 IA content *1 65.1 65.1 65.1 70.0 70.070.0 (IC + ID) content *2 28.7 27.3 31.3 28.7 33.2 27.3 Amount ofsurfactant/ 0% 0% 0% 21% 21% 21% (IC + ID) Particle diameter ratio 0.400.80 0.16 5.00 0.36 2.50 (IC/ID) Foaming property ◯ ◯ ◯ Δ Δ ΔAdhesion-25 25/25 25/25 25/25 10/25 25/25 5/25 Bleeding out ◯ ◯ ◯ Δ ◯ ΔMoisture resistance 25/25 25/25 25/25  0/25 15/25 0/25 Beef tallowresistance ◯ ◯ ◯ X X X *1 IA content = IA/(IA + ID)*100 *2 (IC + ID)content = (IC + ID)/(IC + ID + water)*100

The coating materials of Examples 2-4 to 2-6 are excellent in each ofthe foaming property, initial adhesion, moisture resistance and beeftallow resistance, and no bleeding out was observed, and thus they werefound to be excellent.

Preparation Example 2-9 Preparation of Polypropylene

In the same manner as in Preparation Example 1-1, a catalyst slurry wasobtained.

Then, into an injection stirring type autoclave having an internalcapacity of 24 L, 11 L of toluene, 3.5 mmol of triisobutyl aluminum and2.64 L of liquid propylene were introduced, at room temperature. Theabove catalyst slurry was introduced in its entire amount, then thetemperature was raised to 67° C., and while the total pressure duringthe polymerization was maintained to be constant at 0.65 MPa, stirringwas continued at the same temperature for two hours. After completion ofthe stirring, unreacted propylene was purged to terminate thepolymerization. The autoclave was opened, the toluene solution of thepolymer was recovered in its entire amount, and the solvent and clayresidue were removed to obtain 11 kg of a 13.5 wt % propylene polymertoluene solution (1.5 kg propylene polymer). The weight averagemolecular weight of the obtained polypropylene was 191,000, and thestereoregularity (mmmm) was 45.8%.

Preparation Example 2-10 Preparation of Maleic Anhydride-ModifiedPolypropylene

Into a glass flask equipped with a reflux condenser, a thermometer and astirrer, 650 g of toluene and 350 g of the polypropylene obtained inPreparation Example 2-9 were put, and the interior of the container wasreplaced with nitrogen gas, and the temperature was raised to 110° C.After raising the temperature, 14 g of maleic anhydride was added, and4.7 g of t-butylperoxyisopropyl monocarbonate (Perbutyl I, manufacturedby NOF Corporation) was added, whereupon stirring was continued at thesame temperature for 10 hours to carry out the reaction. Aftercompletion of the reaction, the system was cooled to near roomtemperature, and acetone was added, whereupon the precipitated polymerwas collected by filtration. Further, precipitation with acetone andfiltration were repeated, and the finally obtained polymer was washedwith acetone. The polymer obtained after the washing was dried underreduced pressure to obtain a white powdery modified polymer. Theinfrared absorption spectrum measurement of this modified polymer wascarried out, whereby the content (graft ratio) of maleic anhydridegroups was 1.25 wt % (0.125 mmol/g as maleic anhydride groups, and 0.25mmol/g as calculated as groups represented by —C(═O)O—). Further, theweight average molecular weight was 120,000.

Preparation Example 2-11 Preparation of Maleic Anhydride-ModifiedPolypropylene

The preparation was carried out in the same manner as in PreparationExample 2-2 except that the amount of maleic anhydride was changed to 28g, and the amount of t-butylperoxyisopropyl monocarbonate was changed to9.3 g. The content (graft ratio) of maleic anhydride groups was 2.4 wt %(0.24 mmol/g as maleic anhydride groups, and 0.48 mmol/g as calculatedas —C(═O)O— groups). Further, the weight average molecular weight was100,000.

Preparation Example 2-12 Preparation of Maleic Anhydride-ModifiedPolypropylene

The preparation was carried out in the same manner as in PreparationExample 2-2 except that the amount of maleic anhydride was changed to 21g, and the amount of t-butylperoxyisopropyl monocarbonate was changed to7.0 g. The content (graft ratio) of maleic anhydride groups was 1.6 wt %(0.16 mmol/g as maleic anhydride groups, and 0.32 mmol/g as calculatedas —C(═O)O— groups). Further, the weight average molecular weight was110,000.

Preparation Example 2-13 Preparation of Maleic Anhydride-ModifiedPolypropylene

The preparation was carried out in the same manner as in PreparationExample 2-10 except that the amount of maleic anhydride was changed to105 g, and the amount of t-butylperoxyisopropyl monocarbonate waschanged to 70 g. The content (graft ratio) of maleic anhydride groupswas 5.1 wt % (0.51 mmol/g as maleic anhydride groups, and 1.02 mmol/g ascalculated as —C(═O)O— groups). Further, the weight average molecularweight was 68,000.

Preparation Example 2-14 Preparation of Polyalkylene Glycol-ModifiedPolypropylene Aqueous Dispersion

Into a glass flask equipped with a reflux condenser, a thermometer and astirrer, 30 g of the maleic anhydride-modified polypropylene obtained inPreparation Example 2-10 (content of maleic anhydride groups: 3.75 mmol)and 60 g of toluene were added and completely dissolved by raising thetemperature to 110° C. Then, a solution having 7.5 g of Jeffamine M-1000(7.5 mmol, corresponding to 25 parts by weight of the hydrophilicpolymer (IB) per 100 parts by weight of the propylene polymer (IA))dissolved in 10 g of toluene, was added and reacted at 110° C. for 3hours.

After cooling, toluene was distilled off under reduced pressure toobtain 37 g of the yellow polymer. The infrared absorption analysis ofthe obtained product was carried out, whereby it was observed that apeak corresponding to maleic anhydride in the vicinity of 1,784 cm⁻¹ wasextinct, and the maleic anhydride-modified polypropylene and thepolyether amine were completely bonded. It is in the form of a graftcopolymer having the polyether amine graft-bonded to the maleicanhydride-modified polypropylene.

To 25 g of the obtained yellow polymer, 75 g of THF was added, and thepolymer was completely dissolved at 60° C. At the same temperature, 84 gof pure water was dropwise added thereto over a period of one hour, toobtain a hazy yellow solution. This solution was cooled to 40° C., andby lowering the reduced pressure degree gradually from a reducedpressure degree of 0.03 MPa to 0.0045 MPa, distillation under reducedpressure was carried out until the concentration became 25 wt %, toobtain a translucent slightly yellow resin dispersion. It is consideredthat the dispersed particle sizes are so fine that the dispersion lookstranslucent.

The dispersed particle sizes were measured, whereby the 50% particlediameter was 0.068 μm.

Preparation Example 2-15 Preparation of Polyalkylene Glycol-ModifiedPolypropylene Aqueous Dispersion

44 g of a yellow polymer was obtained in the same manner as inPreparation Example 2-14 except that as the maleic anhydride-modifiedpolypropylene, 30 g of maleic anhydride-modified polypropylene obtainedin Preparation Example 2-11 (content of maleic anhydride groups: 7.2mmol) was used, and 14.4 g of Jeffamine M-1000 (14.4 mmol, correspondingto 48 parts by weight of the hydrophilic polymer (IB) per 100 parts byweight of the propylene polymer (IA)) was used. It is in the form of agraft copolymer having the polyether amine graft-bonded to the maleicanhydride-modified polypropylene.

To 20 g of the obtained yellow polymer, 80 g of THF was added, and thepolymer was completely dissolved at 60° C. At the same temperature, 100g of pure water was dropwise added thereto over a period of one hour, toobtain a yellow solution. This solution was cooled to 40° C., and bylowering the reduced pressure degree gradually from a reduced pressuredegree of 0.03 MPa to 0.0045 MPa, distillation under reduced pressurewas carried out until the concentration became 20 wt %, to obtain atransparent yellow resin dispersion. It is considered that the dispersedparticle sizes are so fine that the dispersion looks almost transparent.

The dispersed particle sizes were measured, whereby the 50% particlediameter was 0.011 μm.

Preparation Example 2-16 Preparation of Polyalkylene Glycol-ModifiedPolypropylene Aqueous Dispersion

Into a glass flask equipped with a reflux condenser, a thermometer and astirrer, 30 g of the maleic anhydride-modified polypropylene obtained inPreparation Example 2-2 (content of maleic anhydride groups: 4.8 mmol)and 70 g of toluene were added and completely dissolved by raising thetemperature to 110° C. Then, a solution having 4.5 g of Jeffamine M-1000(4.5 mmol, corresponding to 15 parts by weight of the hydrophilicpolymer (IB) per 100 parts by weight of the propylene polymer (IA))dissolved in 4.5 g of toluene, was added and reacted at 110° C. for onehour. Then, 0.4 g (4.5 mmol) of morpholine was added and reacted at 110°C. for one hour.

After cooling, toluene was distilled off under reduced pressure toobtain 34 g of the yellow polymer. The infrared absorption analysis ofthe obtained product was carried out, whereby it was observed that 90%of a peak corresponding to maleic anhydride in the vicinity of 1,784cm⁻¹ was extinct, and the maleic anhydride-modified polypropylene andthe polyether amine were completely bonded. It is in the form of a graftcopolymer having the polyether amine graft-bonded to the maleicanhydride-modified polypropylene.

To 25 g of the obtained yellow polymer, 75 g of THF was added, and thepolymer was completely dissolved at 60° C. At the same temperature, 84 gof pure water was dropwise added thereto over a period of one hour, toobtain a hazy yellow solution. This solution was cooled to 40° C., andby lowering the reduced pressure degree gradually from a reducedpressure degree of 0.03 MPa to 0.0045 MPa, distillation under reducedpressure was carried out until the concentration became 25 wt %, toobtain a translucent slightly yellow resin dispersion. It is consideredthat the dispersed particle sizes are so fine that the dispersion lookstranslucent.

The dispersed particle sizes were measured, whereby the 50% particlediameter was 0.086 μm.

Preparation Example 2-17 Preparation of Polyalkylene Glycol-ModifiedPolypropylene Aqueous Dispersion

39 g of a yellow polymer was obtained in the same manner as inPreparation Example 2-14 except that instead of the maleicanhydride-modified polypropylene, the maleic anhydride-modifiedchlorinated polypropylene (manufactured by Toyo Kasei Kogyo Co., Ltd.,the content (graft ratio) of maleic anhydride groups was 2.1 wt % (0.21mmol/g)) was used, and 9 g of Jeffamine M-1000 (9 mmol, corresponding to30 parts by weight of the hydrophilic polymer (IB) per 100 parts byweight of the propylene polymer (IA)) was used. It is in the form of agraft copolymer having the polyether amine graft-bonded to the maleicanhydride-modified chlorinated polypropylene.

To 25 g of the obtained yellow polymer, 75 g of THF was added, and thepolymer was completely dissolved at 60° C. At the same temperature, 100g of pure water and 0.9 g (10 mmol) of 2-amino-2-methyl-1-propanol weredropwise added thereto over a period of one hour, to obtain a yellowsolution. This solution was cooled to 40° C., and by lowering thereduced pressure degree gradually from a reduced pressure degree of 0.03MPa to 0.0045 MPa, distillation under reduced pressure was carried outuntil the concentration became 20 wt %, to obtain a transparent yellowresin dispersion. It is considered that the dispersed particle sizes areso fine that the dispersion looks almost transparent.

The dispersed particle sizes were measured, whereby the 50% particlediameter was 0.072 μm.

Preparation Example 2-18 Preparation of Maleic Anhydride-ModifiedPolypropylene Aqueous Dispersion

Into a glass flask equipped with a reflux condenser, a thermometer and astirrer, 25 g of the maleic anhydride-modified polypropylene obtained inPreparation Example 2-13 (content of maleic anhydride groups: 12.75mmol) and 75 g of THF were added and completely dissolved at 60° C. Tothis solution, 2.3 g (26.0 mmol) of N,N-dimethylethanolamine wasdropwise added, and then at the same temperature, 84 g of pure water wasdropwise added over one hour, to obtain a hazy yellow solution. Thissolution was cooled to 40° C., and by lowering the reduced pressuredegree gradually from a reduced pressure degree of 0.03 MPa to 0.0045MPa, distillation under reduced pressure was carried out until theconcentration became 25 wt %, to obtain a translucent slightly yellowresin dispersion. It is considered that the dispersed particle sizes areso fine that the dispersion looks translucent.

The dispersed particle sizes were measured, whereby the 50% particlediameter was 0.060 μm.

Preparation Example 2-19 Preparation of Maleic Anhydride-ModifiedPropylene Polymer

Into a glass flask equipped with a reflux condenser, a thermometer and astirrer, 650 g of toluene, 175 g of the polypropylene obtained inPreparation Example 2-9 and 175 g of a propylene-1-butene copolymerprepared by means of a metallocene catalyst (Tafiner XM-7070,manufactured by Mitsui Chemicals, Inc., propylene/1-butene=75/25 (molarratio), the weight average molecular weight Mw: 240,000, Mw/Mn=2.2,melting point: 80° C.) were put, and the interior of the container wasreplaced with nitrogen gas, and the temperature was raised to 110° C.After raising the temperature, 35 g of maleic anhydride was added, and17.5 g of t-butylperoxyisopropyl monocarbonate (Perbutyl I, manufacturedby NOF Corporation) was added, whereupon stirring was continued at thesame temperature for 7 hours. After completion of the reaction, in thesame manner as in Preparation Example 2-2, acetone was added, and aprecipitated polymer was collected by filtration to obtain a whitepowdery maleic anhydride-modified polymer. The infrared absorptionspectrum measurement of this modified polymer was carried out, wherebythe content (graft ratio) of the maleic anhydride groups was 2.0 wt %(0.20 mmol/g as calculated as —C(═O)O— groups).

Preparation Example 2-20 Preparation of Aqueous Dispersion ofPolyalkylene Glycol-Modified Propylene Polymer

Into a glass flask equipped with a reflux condenser, a thermometer and astirrer, 30 g of the maleic anhydride-modified propylene polymerprepared in Preparation Example 2-19 and 70 g of toluene were added andcompletely dissolved by raising the temperature to 110° C. Then, asolution having 6.0 g of Jeffamine M-1000 (corresponding to 20 parts byweight of the hydrophilic polymer (IB) per 100 parts by weight of thepropylene polymer (IA)) dissolved in 6.0 g of toluene, was added andreacted at 110° C. for 3 hours. In the same manner as in PreparationExample 2-3, THF was dropwise added thereto, followed by distillationunder reduced pressure to obtain a translucent slightly yellow aqueousresin dispersion. The dispersed particle sizes were so fine that thedispersion looked translucent. The dispersed particle sizes weremeasured, whereby the 50% particle diameter was 0.009 μm, and the 90%particle diameter was 0.011 μm.

Preparation Example 2-21 Preparation of Maleic Anhydride-ModifiedPropylene Polymer

Into a glass flask equipped with a reflux condenser, a thermometer and astirrer, 650 g of toluene and 350 g of a propylene-1-butene copolymerprepared by means of a Ziegler Natta catalyst (Tafiner XR-110T,manufactured by Mitsui Chemicals, Inc., propylene/1-butene=76/24 (molarratio), the weight average molecular weight Mw: 290,000, Mw/Mn=4.1,melting point: 110° C.) were put, and the interior of the container wasreplaced with nitrogen gas, and the temperature was raised to 110° C.After raising the temperature, 35 g of maleic anhydride was added, and17.5 g of t-butylperoxyisopropyl monocarbonate (Perbutyl I, manufacturedby NOF Corporation) was added, whereupon stirring was continued at thesame temperature for 7 hours to carry out the reaction. After completionof the reaction, in the same manner as in Preparation Example 2-2,acetone was added, and a precipitated polymer was collected byfiltration to obtain a white powdery maleic anhydride-modified polymer.The infrared absorption spectrum measurement of this modified polymerwas carried out, whereby the content (graft ratio) of the maleicanhydride groups was 2.1 wt % (0.21 mmol/g as maleic anhydride groups,and 0.42 mmol/g as calculated as —C(═O)O— groups).

Preparation Example 2-22 Preparation of Aqueous Dispersion ofPolyalkylene Glycol-Modified Propylene Polymer

Into a glass flask equipped with a reflux condenser, a thermometer and astirrer, 30 g of the maleic anhydride-modified propylene polymerobtained in Preparation Example 2-21 and 70 g of toluene were added andcompletely dissolved by raising the temperature to 110° C. Then, asolution having 7.5 g of Jeffamine M-1000 (corresponding to 25 parts byweight of the hydrophilic polymer (IB) per 100 parts by weight of thepropylene polymer (IA)) dissolved in 6.0 g of toluene, was added andreacted at 110° C. for 3 hours. In the same manner as in PreparationExample 2-3, THF was dropwise added thereto, followed by distillationunder reduced pressure. The average particle diameter of the obtainedemulsion was very large at a level of at least 1 μm, and precipitateswere substantial, and a good aqueous dispersion was not obtained.

Preparation Example 2-23 Preparation of Aqueous Dispersion ofPolypropylene Modified by Non-Hydrophilic Polymer

37 g of a yellow polymer was obtained in the same manner as in Example2-1 except that to 30 g of the maleic anhydride-modified polypropyleneobtained in Preparation 2-10 (content of maleic anhydride groups: 3.75mmol), 7.5 g of a polyester polyol (P-2010, manufactured by Kuraray Co.,Ltd., molecular weight: 2,000 (nominal value)) (3.75 mmol, correspondingto 25 parts by weight per 100 parts by weight of the polyolefin (IA))and 0.3 g of dimethylbenzylamine were added. It is in the form of agraft copolymer having the polyester polyol graft-bonded to the maleicanhydride-modified polypropylene.

To 20 g of the obtained yellow polymer, 80 g of THF was added, and thepolymer was completely dissolved at 60° C. At the same temperature, 100g of pure water was dropwise added thereto over a period of one hour,whereby the yellow polymer was separated, and no resin dispersion wasobtained.

Here, the polyester polyol employed (P-2010, manufactured by KurarayCo., Ltd.) had an insoluble content of more than 1 wt % when it wasdissolved in water at 25° C. at a concentration of 10 wt % and is not ahydrophilic polymer.

Examples 2-7 to 2-12 Comparative Examples 2-10 to 2-12

To 10 g of each of the resin dispersions (solid content concentration:25 wt) of Preparation Examples shown in Table 2-3, 10 g of thepigment-dispersed paste (solid content concentration: 50 wt %) ofPreparation Example 2-5 and 5.7 g of the aqueous acryl resin dispersionES-20 were added and mixed to prepare a coating material, and theadhesion, water resistance and GH resistance were evaluated.

However, with respect to Comparative Examples 2-11 and 2-12 (PreparationExamples 2-22 and 2-23), the dispersed state was poor, and it wasimpossible to carry out a coating test.

The results are shown in Table 2-3. It is evident that the coatingmaterials of Examples 2-7 to 2-12 are excellent in any of the initialadhesion, moisture resistance and GH resistance.

TABLE 2-3 50% particle Ratio to (ID) Adhesion- Water GH Component (IC)diameter of (IC) particle diameter 100 resistance resistance Ex. 2-7Prep. Ex. 2-14 0.068 μm 0.68 100/100 100/100 >60 min Ex. 2-8 Prep. Ex.2-15 0.011 μm 0.11 100/100 100/100 >60 min Ex. 2-9 Prep. Ex. 2-16 0.086μm 0.68 100/100 100/100 >60 min Ex. 2-10 Prep. Ex. 2-17 0.072 μm 0.72100/100 100/100 >60 min Ex. 2-11 Prep. Ex. 2-18 0.060 μm 0.60 100/100100/100   40 min Ex. 2-12 Prep. Ex. 2-20 0.009 μm 0.09 100/100100/100 >60 min Comp. Ex. 2-10 Prep. Ex. 2-4  0.25 μm 2.5  24/100 16/100 >60 min Comp. Ex. 2-11 Prep. Ex. 2-22 At least 1 μm Impossibleto carry out coating test Comp. Ex. 2-12 Prep. Ex. 2-23 Not emulsifiableImpossible to carry out coating test

Examples Relating to Third Embodiment Preparation Example 3-1Preparation of Polyolefin

In the same manner as in Preparation Example 1-1, a catalyst slurry wasobtained.

Then, into an induction stirring type autoclave having an internalcapacity of 24 L, 11 L of toluene, 3.5 mmol of triisobutyl aluminum and2.64 L of liquid propylene were introduced. At room temperature, theabove catalyst slurry was introduced in its entire amount, then thetemperature was raised to 63° C., and while the total pressure duringthe polymerization was maintained to be constant at 0.65 MPa, stirringwas continued at the same temperature for two hours. After completion ofthe stirring, unreacted propylene was purged to terminate thepolymerization. The autoclave was opened, the toluene solution of thepolymer was recovered in its entire amount, and the solvent and clayresidue were removed to obtain 11 kg of a 12.8 wt % propylene polymertoluene solution (1.4 kg of propylene polymer). The weight averagemolecular weight of the obtained polypropylene was 180,000, and thestereoregularity (mmmm) was 47.5%.

Preparation Example 3-2 Preparation of Maleic Anhydride-ModifiedPolypropylene

Into a glass flask equipped with a reflux condenser, a thermometer and astirrer, 650 g of toluene and 350 g of the polypropylene obtained inPreparation Example 3-1 were put, and the interior of the container wasreplaced with nitrogen gas, and the temperature was raised to 110° C.After raising the temperature, 28 g of maleic anhydride was added, and14 g of t-butylperoxyisopropyl monocarbonate (Perbutyl I, manufacturedby NOF Corporation) was added, whereupon stirring was continued at thesame temperature for 7 hours to carry out the reaction. After completionof the reaction, the system was cooled to near room temperature, andacetone was added, whereupon the precipitated polymer was collected byfiltration. Further, precipitation with acetone and filtration wererepeated, and the obtained polymer was washed with acetone. The polymerobtained after the washing was dried under reduced pressure to obtain awhite powdery maleic anhydride-modified polymer. The infrared absorptionspectrum measurement of this modified polymer was carried out, wherebythe content (graft ratio) of maleic anhydride groups was 2.1 wt % (0.21mmol/g as maleic anhydride groups, and 0.42 mmol/g as reactive groups).Further, the weight average molecular weight was 95,000.

Preparation Example 3-3 Preparation of Polyalkylene Glycol-ModifiedPolypropylene

Into a glass flask equipped with a reflux condenser, a thermometer and astirrer, 30 g of the maleic anhydride-modified polypropylene obtained inPreparation Example 3-2 and 70 g of toluene were added and completelydissolved by raising the temperature to 110° C. Then, a solution having9 g (9 mmol) of Jeffamine M-1000 dissolved in 9 g of toluene, was addedand reacted at 110° C. for 3 hours.

After cooling, toluene was distilled off under reduced pressure toobtain 39 g of a yellow polymer. The infrared absorption analysis of theobtained product was carried out, whereby it was observed that a peakcorresponding to maleic anhydride in the vicinity of 1,784 cm⁻¹ wasextinct, and the maleic anhydride-modified polypropylene and thepolyether amine were completely bonded. It is in the form of a graftcopolymer having the polyether amine graft-bonded to the maleicanhydride-modified polypropylene.

In the following Examples, the operation was carried out underatmospheric pressure (0.101 MPa) unless otherwise specified.

Example 3-1

To 20 g of the polyalkylene glycol-modified polypropylene obtained inPreparation Example 3-3, 80 g of isobutanol (solubility of water at 20°C.: 16.4 wt %) was added, and the polypropylene was completely dissolvedat 100° C. Then, the solution was cooled to 65° C., and at the sametemperature, 120 g of pure water was dropwise added over one hour toobtain a turbidified solution. The operation up to here was carried outunder atmospheric pressure (0.101 MPa).

Then, this liquid was cooled to 40° C., and distillation was initiatedunder a pressure of 0.02 MPa. Further, by lowering the pressuregradually from 0.02 MPa to 0.004 MPa, isobutanol and water weredistilled off until the resin concentration became 25 wt %, to obtain aslightly yellow translucent aqueous resin dispersion. The amount ofisobutanol in the dispersion was not more than 5 wt %. The distilledliquid was 140 g.

The dispersed particle sizes were measured, whereby the 50% particlediameter was 0.015 μm, and the 90% particle diameter was 0.021 μm.Further, the distilled liquid was separated into an upper layer ofisobutanol layer and a lower layer of water layer, and thusliquid-liquid separation was possible. The results are shown in Table3-1.

Example 3-2

An aqueous resin dispersion was obtained in the same manner as inExample 3-1 except that isobutanol was changed to n-butanol (solubilityof water at 20° C.: 20.0 wt %), and the amount of the dropwise addedpure water was changed to 200 g. The state before the distillation was aturbified solution like in Example 3-1. The amount of n-butanol in thedispersion was not more than 10 wt %. The distilled liquid was 220 g.

The dispersed particle sizes were measured, whereby the 50% particlediameter was 0.011 μm, and the 90% particle diameter was 0.015 μm.Further, the distilled liquid was separated into an upper layer ofn-butanol layer and a lower layer of water layer, and thus liquid-liquidseparation was possible.

Comparative Example 3-1

An aqueous resin dispersion was obtained in the same manner as inExample 3-1 except that isobutanol was changed to THF (solubility ofwater at 20° C.: infinite), and the temperature at the time ofdissolution was changed to 65° C. The amount of THF in the dispersionwas not more than 5 wt %. The distilled liquid was 140 g.

The dispersed particle sizes were measured, whereby the 50% particlediameter was 0.011 μm, and the 90% particle diameter was 0.014 μm. Thedistilled layer was uniform layer, and its separation was impossible.

Comparative Example 3-2

This Example was carried out in the same manner as in Example 3-1 exceptthat isobutanol was changed to toluene (solubility of water: 0.05 wt %).As water was dropwise added, the solution became turbid, and finally, asolid substance started to separate. No dispersion was obtained.

Comparative Example 3-3

Into a glass flask equipped with a reflux condenser, a thermometer and astirrer, 20 g of the maleic anhydride-modified polypropylene obtained inPreparation Example 3-2 and 80 g of toluene were put and completelydissolved by raising the temperature to 110° C. Then, after cooling to50° C., 5 g of polyoxyethylene cetyl ether (EMULGEN 220, manufactured byKao Corporation, nonionic surfactant, HLB=14.2) and 5 g ofpolyoxyethylene lauryl ether (EMULGEN 147, manufactured by KaoCorporation, nonionic surfactant, HLB=16.3) were added and dissolved,followed by cooling to 35° C.

100 g of water was added thereto and thoroughly stirred, and then usingan internal shearing type emulsifier Clearmix CLM-0.8S (manufactured byM Technique Co., Ltd.), emulsifying was carried out at 21,000 rpm for 3minutes. Then, into the system, an aqueous solution having2-amino-2-methyl-1-propanol diluted with water to 10 wt %, was added,and the pH was adjusted to 8. From this crude emulsified product,toluene and water were is distilled off by reducing the reduced pressuredegree gradually from a reduced pressure degree of 0.02 MPa to 0.0045MPa at a temperature of 50° C., to obtain a milky white aqueous resindispersion having a concentration of 25 wt %. The amount of toluene inthe dispersion was not more than 5 wt %.

The dispersed particle sizes were measured, whereby the 50% particlediameter was 0.25 μm, and the 90% particle diameter was 3.1 μm. Further,distilled liquid was separated into an upper layer of toluene layer anda lower layer of water layer, and liquid-liquid separation was possible.

TABLE 3-1 Solvent Dispersed particle sizes Solubility of 50% Particle90% Particle Liquid-liquid water at diameter diameter separation of Type20° C. (μm) (μm) distilled liquid Ex. 3-1 Isobutanol 16.4 0.015 0.021 ∘Ex. 3-2 n-butanol 20.0 0.011 0.015 ∘ Comp. Ex. 3-1 THF Infinite 0.0110.014 x Comp. Ex. 3-2 Toluene  0.05 No dispersion obtained Not distilledComp. Ex. 3-3 Toluene  0.05 0.25  3.1  ∘ (Surfactant used)

Examples Relating to Fourth Embodiment Preparation Example 4-1Preparation of Polyolefin

In the same manner as in Preparation Example 1-1, a catalyst slurry wasobtained.

Then, into an induction stirring type autoclave having an internalcapacity of 24 L, 11 L of toluene, 3.5 mmol of triisobutyl aluminum and2.64 L of liquid propylene were introduced. At room temperature, theabove catalyst slurry was introduced in its entire amount, then thetemperature was raised to 63° C., and while the total pressure duringthe polymerization was maintained to be constant at 0.65 MPa, stirringwas continued at the same temperature for two hours. After completion ofthe stirring, unreacted propylene was purged to terminate thepolymerization. The autoclave was opened, the toluene solution of thepolymer was recovered in its entire amount, and the solvent and clayresidue were removed by No. 60 filter paper manufactured by ADVANTECCompany, to obtain 11 kg of a 11.5 wt % propylene polymer toluenesolution (1.26 kg of propylene polymer). The weight average molecularweight of the obtained polypropylene was 197,000, and thestereoregularity (mmmm) was 46.2%.

Preparation Example 4-2 Preparation of Maleic Anhydride-ModifiedPolypropylene

A reflux condenser, a thermometer and a stirrer were attached to a 5 Lglass flask equipped with a bottom-discharge cock and an oil-circulationjacket, and 3.04 kg of the toluene solution of the polypropyleneobtained in Preparation Example 4-1 was put, and the temperature wasraised to 60° C., and the pressure was gradually reduced to 0.06 MPa toremove 2.04 kg of toluene, whereupon nitrogen was introduced to returnthe pressure to normal pressure to obtain 1 kg of a toluene solutioncontaining 35 wt % of the polypropylene.

The interior of the container was replaced with nitrogen gas, and thetemperature was raised to 110° C., then 21 g of maleic anhydride wasadded, and 7 g of t-butylperoxyisopropyl monocarbonate (Perbutyl I,manufactured by NOF Corporation) was added, whereupon stirring wascontinued at the same temperature for 10 hours to carry out thereaction. By the infrared absorption spectrum analysis, it was observedthat the absorption by the double bond of maleic anhydride in thevicinity of 830 cm⁻¹ was extinct upon expiration of 10 hours, and allsuch double bonds were reacted. Further, a part of the reaction solutionwas sampled, and acetone was added for precipitation, and further,precipitation with acetone and filtration were repeated to remove theunreacted and by-products to obtain a maleic anhydride-modified polymer.The infrared absorption spectrum measurement of this modified polymerwas carried out, whereby the content (graft ratio) of maleic anhydridegroups was 1.5 wt % (0.15 mmol/g as maleic anhydride groups, and 0.30mmol/g as reactive groups). Further, the weight average molecular weightwas 110,000.

After completion of the reaction, 0.4 kg of toluene was added, followedby cooling to bring the liquid temperature to 60° C.

2.1 kg of warm water of 60° C. was added thereto, and the mixture wasstirred for 30 minutes at a rotational speed of 300 rpm and then left tostand for 10 minutes, whereby it was separated into an upper layer oftoluene layer and a lower layer of water layer, and from the bottomdischarge cock, water was withdrawn (water washing step). This waterwashing step was further repeated four times, whereby a total of 9.9 kgof acidic waste water (94% recovery) was withdrawn. Then, using aDean-Stark dehydration apparatus, dehydration operation was carried outat a jacket temperature of 140° C. Further, when the internaltemperature became 113° C., the dehydration operation was carried outfor 3 hours. Then, 230 g of toluene was distilled off to obtain 1,170 gof a toluene solution of the maleic anhydride-modified polypropylene (30wt %).

Preparation Example 4-3 Preparation of Polyalkylene Glycol-ModifiedPolypropylene

Into a glass flask equipped with a reflux condenser, a thermometer and astirrer, 500 g (solid content: 150 g) of the toluene solution of themaleic anhydride-modified polypropylene obtained in Preparation Example4-2 was added, and the temperature was raised to 110° C. Then, asolution having 45 g (45 mmol) of Jeffamine M-1000 dissolved in 45 g oftoluene, was added and reacted at 110° C. for 3 hours.

A small amount of the reaction product was taken, and toluene wasdistilled off under reduced pressure to obtain a sample, and withrespect to the sample, the infrared absorption spectrum analysis wascarried out, whereby it was observed that a peak corresponding to maleicanhydride in the vicinity of 1,784 cm⁻¹ was extinct, and the maleicanhydride-modified polypropylene and the polyether amine were completelybonded. It is in the form of a graft copolymer having the polyetheramine graft-bonded to the maleic anhydride-modified polypropylene.

Preparation Example 4-4 Preparation of Polyalkylene Glycol-ModifiedPolypropylene

Into a glass flask equipped with a reflux condenser, a thermometer and astirrer, 500 g (solid content: 150 g) of the toluene solution of themaleic anhydride-modified polypropylene obtained in Preparation Example4-2 was added, and the temperature was raised to 110° C. Then, asolution having 30 g (30 mmol) of Jeffamine M-1000 dissolved in 30 g oftoluene, was added and reacted at 110° C. for one hour. Further, 2.6 g(30 mmol) of morpholine was added and reacted at 110° C. for one hour.

A small amount of the reaction product was taken, and toluene wasdistilled off under reduced pressure to obtain a sample, and withrespect to the sample, the infrared absorption spectrum analysis wascarried out, whereby it was observed that 90% of a peak corresponding tomaleic anhydride in the vicinity of 1,784 cm⁻¹ was extinct, and themaleic anhydride-modified polypropylene and the polyether amine werecompletely bonded. It is in the form of a graft copolymer having thepolyether amine graft-bonded to the maleic anhydride-modifiedpolypropylene.

In the following Examples, operations were carried out under atmosphericpressure (0.101 MPa) unless otherwise specified.

Example 4-1

While 100 g of the toluene solution (solid content: 33 wt %) of thepolyalkylene glycol-modified polypropylene obtained in PreparationExample 4-3 was heated to 60° C. and stirred, a mixed liquid comprising120 g of isopropanol (solubility of water at 20° C.: infinite) and 30 gof water, was dropwise added over one hour at 65° C. A slightly yellowhazy liquid was obtained. Further, a mixed liquid comprising 30 g ofisopropanol and 160 g of water was dropwise added over one hour, whilethe internal temperature was maintained to be 65° C., to obtain atranslucent yellow liquid. Here, the solubility of water in toluene at20° C. is 0.05 wt %.

Then, this liquid was cooled to 40° C., and distillation was initiatedunder a pressure of 0.02 MPa. Further, by lowering the pressuregradually from 0.02 MPa to 0.004 MPa, toluene, isopropanol and waterwere distilled off until the resin concentration became 25 wt %, toobtain a slightly yellow translucent aqueous resin dispersion. The totalamount of toluene and isopropanol in the dispersion was not more than 5wt %. The distilled liquid was 308 g.

The dispersed particle sizes were measured, whereby the 50% particlediameter was 0.028 μm, and the 90% particle diameter was 0.046 μm. Theresults are shown in Table 4-1.

Example 4-2

While 100 g of the toluene solution (solid content: 33 wt %) of thepolyalkylene glycol-modified polypropylene obtained in PreparationExample 4-3 was heated to 60° C. and stirred, a mixed liquid comprising120 g of isopropanol (solubility of water at 20° C.: infinite) and 30 gof water, was dropwise added over one hour at 65° C. A slightly yellowhazy liquid was obtained. Then, this liquid was cooled to 45° C., anddistillation was initiated under a pressure of 0.02 MPa. Further, bylowering the pressure gradually from 0.02 MPa to 0.008 MPa, toluene,isopropanol and water were distilled off in a total amount of 160 guntil the resin concentration became 33 wt %.

Then, a mixed liquid comprising 18 g of isopropanol and 162 g of waterwas dropwise added for one hour at 65° C. to obtain a translucent yellowsolution. Then, this solution was cooled to 45° C., and distillation wasinitiated under a pressure of 0.02 MPa. Further, by lowering thepressure gradually from 0.02 MPa to 0.004 MPa, toluene, isopropanol andwater were distilled off until the resin concentration became 25 wt %,to obtain a slightly yellow translucent aqueous resin dispersion. Thedistilled water was 148 g. The total amount of toluene and isopropanolin the dispersion was not more than 5 wt %.

The dispersed particle sizes were measured, whereby the 50% particlediameter was 0.030 μm, and the 90% particle diameter was 0.049 μm.

Example 4-3

An aqueous resin dispersion was obtained in the same manner as inExample 4-1 except that the toluene solution (solid content: 33 wt %) ofthe polyalkylene glycol-modified polypropylene obtained in PreparationExample 4-4 was used. The total amount of toluene and isopropanol in thedispersion was not more than 5 wt %.

The dispersed particle sizes were measured, whereby the 50% particlediameter was 0.048 μm, and the 90% particle diameter was 0.079 μm.

Example 4-4

An aqueous resin dispersion was obtained in the same manner as inExample 4-2 except that the toluene solution (solid content: 33 wt %) ofthe polyalkylene glycol-modified polypropylene obtained in PreparationExample 4-4 was used. The total amount of toluene and isopropanol in thedispersion was not more than 5 wt %.

The dispersed particle sizes were measured, whereby the 50% particlediameter was 0.055 μm, and the 90% particle diameter was 0.088 μm.

Comparative Example 4-1

Into a glass flask equipped with a reflux condenser, a thermometer and astirrer, 60 g (solid content: 18 g) of the toluene solution of themaleic anhydride-modified polypropylene obtained in Preparation Example4-2 and 40 g of toluene were added, and the temperature was raised to50° C. Then, 5 g of a polyoxyethylene cetyl ether (EMULGEN 220,manufactured by Kao Corporation, nonionic surfactant, HLB=14.2) and 5 gof a polyoxyethylene lauryl ether (EMULGEN 147, manufactured by KaoCorporation, nonionic surfactant, HLB=16.3) were added and dissolved,followed by cooling to 35° C.

100 g of water was added thereto and thoroughly stirred, and then usingan internal shearing type emulsifier Clearmix CLM-0.8S (manufactured byM Technique Co., Ltd.), emulsifying was carried out at 21,000 rpm for 3minutes. Then, into the system, an aqueous solution having2-amino-2-methyl-1-propanol diluted with water to 10 wt %, was added,and the pH was adjusted to 8. From this crude emulsified product,toluene and water were distilled off by reducing the reduced pressuredegree gradually from a reduced pressure degree of 0.02 MPa to 0.0045MPa at a temperature of 50° C., to obtain a milky white aqueous resindispersion having a concentration of 25 wt %. The amount of toluene inthe dispersion was not more than 5 wt %.

The dispersed particle sizes were measured, whereby the 50% particlediameter was 0.4 μm, and the 90% particle diameter was 5 μm.

TABLE 4-1 Dispersed particle sizes 50% Particle 90% Particle diameter(μm) diameter (μm) Ex. 4-1 0.028 0.046 Ex. 4-2 0.030 0.049 Ex. 4-3 0.0480.079 Ex. 4-4 0.055 0.088 Comp. Ex. 4-1 0.4 5

The entire disclosures of Japanese Patent Application No. 2005-164597filed on Jun. 3, 2005, Japanese Patent Application No. 2005-199454 filedon Jul. 7, 2005, Japanese Patent Application No. 2006-039898 filed onFeb. 16, 2006 and Japanese Patent Application No. 2006-092591 filed onMar. 29, 2006 including specifications, claims, drawings and summariesare incorporated herein by reference in their entireties.

1. An aqueous resin dispersion which has particles made of a polymer(IC) comprising a propylene polymer (IA) and particles made of at leastone resin (ID) selected from the group consisting of an acrylic resin, apolyester resin, a polyurethane resin, an epoxy resin and a vinyl esterresin, respectively dispersed in water, and which satisfies thefollowing (1) to (4): (1) the weight ratio of the propylene polymer (IA)to the resin (ID) is from 90:10 to 10:90, (2) the weight ratio of thetotal amount of the polymer (IC) and the resin (ID) to water is from5:95 to 60:40, (3) the content of a surfactant is at most 10 parts byweight per 100 parts by weight of the total amount of the polymer (IC)and the resin (ID), and (4) the 50% particle diameter of the particlesmade of the polymer (IC) is at most 0.5 μm and at most 0.9 time of the50% particle diameter of the particles of the resin (ID).
 2. The aqueousresin dispersion according to claim 1, wherein the polymer (IC) is apolymer having a hydrophilic polymer (IB) bonded to the propylenepolymer (IA) in a ratio of (IA):(IB)=100:5 to 100:500 (weight ratio). 3.The aqueous resin dispersion according to claim 2, wherein the polymer(IC) is a polymer having the hydrophilic polymer (IB) bonded in anamount of from 0.01 to 5 mmol per 1 g of the propylene polymer (IA). 4.The aqueous resin dispersion according to claim 2, wherein the polymer(IC) is a graft copolymer having a hydrophilic polymer (IB) graft-bondedto the propylene polymer (IA).
 5. The aqueous resin dispersion accordingto claim 2, wherein the polymer (IC) is a polymer having a carboxylicacid derivative group bonded to the propylene polymer (IA) in an amountof from 0.01 to 5 mmol/g as calculated as a group represented by—C(═O)O— and wherein the hydrophilic polymer (IB) is bonded to thecarboxylic acid derivative group.
 6. The aqueous resin dispersionaccording to claim 2, wherein the hydrophilic polymer (IB) is apolyether resin having an amino group.
 7. The aqueous resin dispersionaccording to claim 1, wherein the polymer (IC) is one having acarboxylic acid derivative group bonded to the propylene polymer (IA).8. The aqueous resin dispersion according to claim 1, wherein thepropylene polymer (IA) is a stereo-block polypropylene polymer havingisotactic blocks and atactic blocks.
 9. The aqueous resin dispersionaccording to claim 8, wherein the propylene polymer (IA) is astereo-block polypropylene polymer comprising isotactic blocks andatactic blocks, and when peaks derived from the carbon atom of a methylgroup of a propylene unit chain portion of a head-to-tail linkage, areobserved by ¹³C-NMR and the chemical shift of a peak top of a peakattributable to a pentad represented by mmmm is set to be 21.8 ppm, theratio (S₁/S) of the area S₁ of a peak having a peak top at 21.8 ppm tothe total area S of peaks appearing from 19.8 ppm to 22.1 ppm, is from20% to 70%, and when the area of a peak (mmmr) having a peak top from21.5 to 21.7 ppm is represented by S₂, 4+2S₁/S₂>5.
 10. The aqueous resindispersion according to claim 1, wherein the propylene polymer (IA) is apropylene-1-butene copolymer having a propylene content of from 50 mol %to 95 mol %, and the copolymer (IA) has a molecular weight distributionMw/Mn of at most 3.0 and a melting point Tm of at most 120° C.
 11. Theaqueous resin dispersion according to claim 1, wherein the propylenepolymer (IA) is produced by using a metallocene catalyst.
 12. Theaqueous resin dispersion according to claim 1, which further comprises apigment (IE), wherein the weight ratio of the total amount of thepolymer (IC) and the resin (ID) to the pigment (IE) is from 100:10 to100:400.
 13. A coating material made of the aqueous resin dispersion asdefined in claim
 1. 14. A laminate having formed on a thermoplasticresin-molded product (IF) a layer comprising a polymer (IC) comprising apropylene polymer (IA) and at least one resin (ID) selected from thegroup consisting of an acrylic resin, a polyester resin, a polyurethaneresin, an epoxy resin and a vinyl ester resin in a weight ratio of(IA):(ID)=90:10 to 10:90 and having a surfactant content of at most 10parts by weight per 100 parts by weight of the total amount of thepolymer (IC) and the resin (ID).
 15. A laminate having a resin layerformed by applying and heating the aqueous resin dispersion as definedin claim 1, on a thermoplastic resin-molded product (IF).